Hydroprocessing of heavy hydrocarbon feeds using small pore catalysts

ABSTRACT

Heavy oil feeds are hydroprocessed in the presence of a solvent and in the presence of a catalyst with a median pore size of about 85 Å to about 120 Å under conditions that provide a variety of benefits. The solvent can be an added solvent or a portion of the liquid effluent from hydroprocessing. The processes allow for lower pressure processing of heavy oil feeds for extended processing times or extended catalyst lifetimes be reducing or mitigating the amount of coke formation on the hydroprocessing catalyst.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 61/529,565 filed Aug. 31, 2011, herein incorporated by reference inits entirety.

FIELD OF THE INVENTION

This invention is directed to a process for producing a hydroprocessedproduct from residua or heavy hydrocarbon feeds.

BACKGROUND

Crude oil is typically distilled to produce a variety of components thatcan be used directly as fuels or that are used as feedstocks for furtherprocessing or upgrading. In what is known as atmospheric distillation, aheavy residuum is produced typically that has an initial boiling pointof about 650° F. (343° C.). This residuum is typically referred to asatmospheric residuum or as an atmospheric residuum fraction.

Atmospheric residuum fractions tend to collect a relatively highquantity of various metals, sulfur components and nitrogen componentsrelative to the lighter distillation fractions as a result of thedistillation process. Because these metal, sulfur and nitrogencomponents are relatively undesirable in various fuels, they aretypically removed by various catalytic hydroprocessing techniques.

In some instances, the atmospheric residuum is further distilled undervacuum, i.e., at a pressure below atmospheric pressure, to recoveradditional distillation fractions. At vacuum conditions, additionallighter fractions can be recovered without adding to various problemsencountered in atmospheric distillation such as coking of the heavyfraction components. The heavy residuum recovered in vacuum distillationof the atmospheric residuum is typically referred to as vacuum residuumor a vacuum residuum fraction, and typically has an initial boilingpoint of about 1050° F. (566° C.). This vacuum residuum is generallyhigher in metals, sulfur components and nitrogen components thanatmospheric residuum, and as was the case with atmospheric residuum,removal of these components can be carried out by catalytichydroprocessing.

Catalytic hydroprocessing of atmospheric and vacuum residua is carriedout in the presence of hydrogen, using a hydroprocessing catalyst. Insome processes, hydroprocessing of residua is carried out by adding adiluent or solvent.

U.S. Pat. No. 3,617,525 discloses a process for removing sulfur from ahydrocarbon fraction having a boiling point above about 650° F. (343°C.). In carrying out the process, the hydrocarbon fraction is separatedinto a gas oil fraction having a boiling point between about 650° F.(343° C.) and about 1050° F. (566° C.), and a heavy residuum fractionboiling above about 1050° F. (566° C.). The gas oil fraction iscatalytically hydrodesulfurized until the gas oil fraction contains lessthan 1 percent sulfur. The hydrodesulfurized gas oil is then used todilute the heavy residuum fraction, and the diluted heavy residuumfraction is catalytically hydrodesulfurized, producing fuels or fuelblending components reduced in sulfur content. The process is consideredto provide an increased catalyst life and to use a smaller reactorvolume compared to typical processes.

U.S. Pat. No. 4,302,323 discloses a process for upgrading a residualpetroleum fraction in which the residual fraction is mixed with a lightcycle oil and hydrogen and the mixture sent through a catalytichydrotreating zone containing a hydrotreating catalyst and then ahydrocracking zone containing a hydrocracking catalyst. Upgradedproducts are then separated from the effluent of the hydrocracking zone.The light cycle oil boils in the range of from 400° F. (204° C.) to 700°F. (371° C.), has a high aromatic content, and is high in nitrogen. Itis considered that the light cycle oil acts more as a diluent ratherthan as a hydrogen donor and that the addition of the light cycle oilresulted in a substantial increase in the yield of premium products suchas distillate fuels.

U.S. Pat. No. 4,421,633 discloses a combination hydrodesulfurization andhydrocracking process. The feedstock can be atmospheric residuum orvacuum residuum, which is mixed with a solvent that is a recycleddistillate boiling at about 400° F.-700° F. (204° C.-371° C.),considered to be equivalent to a FCC light cycle oil. The process uses amixture of large pore and small pore catalysts such as large pore andsmall pore sulfided Ni—W catalysts. The large pore catalyst has a medianpore diameter of 180 Å, while the small pore catalyst has a median porediameter of about 60 Å with no pores larger than 80 Å. The processconverts the higher boiling point residua to lower boiling pointhydrocarbons by forming distillate and naphtha while removingheteroatoms, metals and carbon residuals from the higher boiling pointresidua. It is noted that the description also includes examples whereno solvent is used. The desulfurization activity in examples withoutsolvent appears to be comparable or superior to the desulfurizationactivity for the examples that include a solvent.

U.S. Pat. No. 4,585,546 describes a method for hydrotreating petroleumheavy ends in aromatic solvents with large pore size alumina. Themethods include processing resids mixed with a solvent such asortho-xylene or a light cycle oil at 1000 psig (5.5 MPag) and 350° C.The resids were hydroprocessed in the presence of either a commercialhydrodesulfurization catalyst with a median pore size of 70 Å to 80 Å ora hydrodesulfurization catalyst with an alumina support having a medianpore size of about 220 Å. The larger pore catalyst was shown to havehigher activity for metals removal and comparable activity for sulfurremoval as compared to the smaller pore catalyst.

There is a need to further develop processes for hydroprocessing heavyhydrocarbon oils to produce fuel grade products. It is also particularlydesirable to provide hydroprocessing processes with improved selectivityto desired products. For example, it is desirable to providehydroprocessing processes that crack molecules boiling at or above 1050°F. (566° C.) (also referred to as a “1050° F.+ (566° C.+) fraction”herein) into molecules boiling below 1050° F. (566° C.) (also referredto as a “1050° F.⁻ (566° C.⁻) fraction” herein), while minimizing theformation of “C₄ ⁻” hydrocarbon compounds (i.e., hydrocarbon compoundshaving four carbons or less), and coke byproducts.

SUMMARY OF THE PREFERRED EMBODIMENTS OF THE INVENTION

In various embodiments, systems and methods are provided forhydroprocessing of heavy oil feeds. In one embodiment, a process forproducing a hydroprocessed product includes exposing a combinedfeedstock comprising a heavy oil feed component and a solvent componentto a hydroprocessing catalyst comprising a Group VIII non-noble metaland a Group VI metal and having a median pore size of about 85 Å toabout 120 Å, such as 85 Å to about 100 Å, under effectivehydroprocessing conditions to form a hydroprocessed effluent, theeffective hydroprocessing conditions including a total pressure of about1500 psig (10.3 MPag) or less, such as a hydrogen partial pressure ofabout 1000 psia (6.9 MPa) or less, and a liquid hourly space velocity ofthe fraction of the combined feedstock boiling above 1050° F. of atleast about 0.10 hr⁻¹, such as at least about 0.12 hr⁻¹; separating thehydroprocessing effluent to form at least a liquid effluent; andfractionating a first portion of the liquid effluent to form at least adistillate product and a bottoms product, the bottoms product having aT5 boiling point of about 600° F. The effective hydroprocessingconditions can also include a temperature of at least about 360° C.and/or less than about 510° C., such as about 380° C. to about 460° C.

The solvent can be in the form of an added solvent, in the form of arecycled portion of the liquid effluent from hydroprocessing, or acombination thereof. Optionally, a portion of the bottoms product, suchas a second bottoms product from a reduced pressure distillation, can beprocessed via solvent deasphalting to form a deasphalted oil fractionand a deasphalting residue or asphalt fraction.

In some embodiments, hydroprocessing conditions effective for conversionof at least about 90% of the feedstock relative to a conversiontemperature of 1050° F. (566° C.), including a hydroprocessingtemperature of at least about 420° C., can be used to form a bottomsproduct with an increased amount of wax relative to the feedstock. Instill other embodiments, hydroprocessing conditions effective forconversion of at least about 80% of the feedstock relative to aconversion temperature of 1050° F. and for 75% desulfurization of thefeedstock can be used to form a bottoms product having a sulfur contentof about 1 wt % or less.

In another embodiment, a process for producing a hydroprocessed productincludes exposing a combined feedstock comprising a heavy oil feedcomponent and a solvent component to a hydroprocessing catalyst undereffective hydroprocessing conditions to form a hydroprocessed effluent,the effective hydroprocessing conditions including a hydrogen partialpressure of about 1000 psia (6.9 MPa) or less, such as 800 psia (5.5MPa) or less, a temperature of at least about 360° C., such as about380° C. to 510°, and optionally at least about 420° C., and a liquidhourly space velocity of the fraction of the combined feedstock boilingabove 1050° F. (566° C.) of at least about 0.10 hr⁻¹, such as at leastabout 0.12 hr⁻¹; separating the hydroprocessing effluent to form atleast a liquid effluent; and fractionating a first portion of the liquideffluent to form at least a distillate product and a bottoms product,the bottoms product having the bottoms product having an ASTM D6352 10%distillation point of at least about 600° F. (316° C.).

In various aspects where the solvent component includes a recyclecomponent, the ratio of the heavy oil feed component and the recyclecomponent can be from about 0.3 to about 6.0, such as from about 0.5 toabout 5.0.

BRIEF DESCRIPTION OF THE DRAWINGS

The attached Figures represent alternative embodiments of the overallinvention, as well as comparative examples. The Figures pertaining tothe invention are intended to be viewed as exemplary embodiments withinthe scope of the overall invention as claimed.

FIG. 1 shows a first preferred configuration of the process of theinvention for performing hydroprocessing on a heavy oil feed.

FIG. 2 shows a second preferred configuration of the process of theinvention for performing hydroprocessing on a heavy oil feed.

FIG. 3 shows a third preferred configuration of the process of theinvention for performing hydroprocessing on a heavy oil feed.

FIG. 4 shows a fourth preferred configuration of the process of theinvention for performing hydroprocessing on a heavy oil feed.

DETAILED DESCRIPTION

Overview

In various aspects according to the invention, processes are providedfor producing a hydroprocessed product. The process is capable oftreating residua or heavy hydrocarbon oils to produce a hydroprocessedoil product that has reduced sulfur, nitrogen, metals and “1050° F.+(566° C.+) components” (i.e., components that boil at 1050° F. (566° C.)and above) relative to the heavy oil. In some aspects, processing ofheavy oils is facilitated by recycling a portion of the total liquideffluent from conversion of the heavy oil for use as a solvent as partof the input to the heavy oil hydroprocessing reaction. In otheraspects, processing of heavy oils is facilitated by using a separatesolvent as part of the input to the heavy oil hydroprocessing reaction.In still other aspects, the solvent component contains at least onesingle-ring aromatic compound. In aspects where the solvent componentcontains at least one single-ring aromatic compound, the solventcomponent preferably has an ASTM D86 10% distillation point of at least120° C. (248° F.) and a 90% distillation point of not greater than 300°C. (572° F.).

Depending on the embodiment, various advantages can be achievedaccording to the invention. One difficulty encountered during heavy oilprocessing is short catalyst lifetimes. Due to the nature of heavy oilfeeds, conventional processing of heavy oil feeds tends to result incoking of hydroprocessing catalysts. Heavy oil feeds also typicallycontain high concentrations of metals that can further contribute todeactivation of hydroprocessing catalysts. In order to overcome thesedifficulties, catalysts with large pore size supports have been usedconventionally for processing of heavy feeds, such as catalysts withpore sizes of 150 Å or more, as such catalysts are believed to providesuperior lifetime. Part of the enhanced lifetime of these larger porecatalysts was believed to be due to the ability of such catalysts toremove metals from a heavy oil feed while avoiding concentration of suchmetals at the surface of the catalyst. Additionally, high partialpressures of hydrogen have been used to mitigate the deposition of cokeon the catalyst.

In various aspects of the present invention, hydroprocessing withimproved catalyst lifetime can be performed by incorporating a solventinto a heavy oil feed. By using the solvent, the feed can behydroprocessed in the presence of a hydroprocessing catalyst attemperatures of at least about 360° C. and at hydrogen partial pressuresof about 1000 psig (6.9 MPag) or less, such as about 800 psig (5.5 MPag)or less. During hydroprocessing under these reaction conditions,reactions associated with thermal cracking can also take place in thereaction environment. Conventionally, such reaction conditions wouldlead to severe coking of a catalyst, resulting in short catalystlifetime. Use of a suitable solvent allows for extended catalystlifetime white processing under such hydroprocessing conditions.

Additionally or alternately, in some aspects of the present inventionmethods are provided for achieving a desired level of desulfurizationand removal of other contaminants from a feed while reducing the amountof aromatic saturation. This allows for increased contaminant removalwithout a corresponding increase in consumption of hydrogen by moleculeswith low hydrogen to carbon ratios.

Conventionally, processing of heavy oil fractions has requiredprocessing at hydrogen pressures of at least 1500 psig (10.3 MPag) and alarge ratio of hydrogen treat gas to feedstock flow. Under theseconditions, hydrogen can be consumed by a variety of side reactions thatmay not be desirable. For example, some polynuclear aromatic (PNA) coreshave a low ratio of hydrogen to carbon, and a substantial hydrogeninvestment is required to convert such PNA cores to distillate ornaphtha fuels. More generally, the excess of hydrogen required undertypical conditions results in saturation of a variety of aromaticmolecules that may not need hydrogenation to be included in a beneficialproduct fraction. As a result, the consumption of hydrogen duringconventional processing of heavy oils can be high relative to thestoichiometric need for desired reactions. By reducing the amount ofaromatic saturation that occurs at a given level of feed conversion, theratio of hydrogen consumed by desired reactions versus hydrogen consumedby side reactions can be increased. In some aspects, the decrease in therelative amount of aromatic saturation is facilitated by use of a smallpore hydroprocessing catalyst.

In still other aspects, methods are provided for separating outmolecules with low hydrogen to carbon ratios from higher value moleculesat reduced levels of conversion of the heavy components. In a typicalheavy oil feedstock, a portion of the heavy oil feedstock can correspondto molecules with high molecular weight and low hydrogen to carbonratios, such as asphaltenes or other polynuclear aromatics. These lessdesirable molecules, however, have similar boiling ranges to somemolecules that are desirable from a processing standpoint, such asmolecules with higher hydrogen to carbon ratios. One method forrecovering the desirable molecules is to subject a heavy oil feed tohydroprocessing conditions capable of converting a high percentage ofthe 1050° C.+ (566° C.+) portion of the feed, such as conditionssuitable for converting at least 80 wt % of the 1050° F.+ (566° C.+)portion of the feed to components with a boiling point of less than1050° F. (566° C.). Under these severe hydroprocessing conditions, themore desirable molecules can be converted to lower boiling pointspecies, but typically at the cost of subjecting the entire teed to moresevere conditions. This additional severity can lead to bothover-conversion of desirable products to lower value species, excessconsumption of hydrogen by aromatic saturation of less desirablemolecules, and rapid catalyst deactivation. Conventionally, low valuemolecules are removed from a fraction containing higher value moleculesby converting a large percentage of the low value molecules via additionof hydrogen, such as conversion of at least about 80 wt % of thecomponent compounds in the feed that have boiling points of 1050° F.(566° C.) or greater. The remaining unconverted portion of the teed,containing primarily lower value compounds, can then be separated out asa bottoms portion during a fractionation. While this increases thehydrogen content of the low value molecules, it is often an undesirableprocess in terms of the amount of hydrogen (and other costs) required toupgrade the low value molecules in comparison with the resulting valueof the upgraded molecules.

In contrast to conventional methods, various aspects of the inventiondescribed herein allow for hydroprocessing of a feed to achieve a lowerlevel of conversion, such as conversion of about 50 wt % to about 70 wt% of the portion of the feed that boils at 1050° F. (566° C.) orgreater. This reduces the number of low value molecules that areupgraded using hydrogen. Instead of performing further feed conversionto capture the remaining higher value (i.e., higher hydrogen to carbonratio) molecules while rejecting the lower value molecules, theunconverted portion of the teed is then exposed to a solventdeasphalting process. This allows for separation of molecules with lowhydrogen to carbon ratios as the residual side product from thedeasphalting process. The hydrogen to carbon ratio of the molecules inthe residual side product from deasphalting can be similar to thehydrogen to carbon ratio of the bottoms product from a higher severityhydroconversion process.

Additionally or alternately, in some aspects processes are provided forusing small pore hydroprocessing catalysts for hydroprocessing of theheavy oil. Hydroprocessing catalysts with median pore diameters of about85 Å to about 120 Å have conventionally been used for hydroprocessing oflower boiling feedstocks, such as distillate feeds. However, suchsmaller pore catalysts have not traditionally been used for heavy oilprocessing due to poor catalyst lifetime and difficulties with pluggingof catalyst beds in fixed bed reactors. By recycling a portion of thetotal liquid effluent from hydroprocessing of the heavy oil and/or usinga suitable solvent, it has been discovered that smaller pore catalystscan be used while maintaining improved catalyst lifetimes for theprocessing.

In yet other aspects of the invention, processes are provided that allowfor creation of beneficial products from hydroprocessing of a heavy oilfraction. For example, a heavy oil fraction can be hydroprocessed andthen fractionated to form a bottoms fraction that is enriched in wax.Such a product can be suitable, for example, for use as a feed in a waxproduction plant. This can allow a less valuable bottoms product to beused in place of a (typically) more valuable vacuum gas oil product asthe feed for wax production.

As still another example, a heavy oil fraction can be hydroprocessed toproduce a low sulfur fuel oil. Historically, little or no restrictionhas been placed on the sulfur content of bunker fuel or fuel oil. Thisallowed heavy oil fractions with sulfur contents as high as 4 wt % or 5wt % to be sold as fuel oils. However, current and future regulationsmay restrict the sulfur content of fuel oils to lower values. Due tosuch tighter sulfur content restrictions, fuel oils with reduced sulfurcontents will become increasingly valuable. In some embodiments,processing a heavy oil fraction according to the invention can allow forproduction of a bottoms fraction from a vacuum tower into a fuel oil, ormore specifically a Bunker C Fuel Oil, with a sulfur content of lessthan about 1 wt %, or even less than about 0.1 wt %. Such a low sulfurfuel oil is valuable for use as a fuel or for blending with other fueloil fractions to reduce the overall sulfur content of a blend of fueloil fractions. Bunker C Fuel Oils are typically used as maritimeshipping fuels and are heavy fuels that typically have a widedistillation range of about 575 to 1500° F. (302 to 816° C.), withusually more than about 75 wt % boiling above about 750° F. (399° C.).

Definitions

In order to clarify the description of the invention, the followingdefinitions are provided. The following definitions should be appliedthroughout the description herein unless otherwise specified.

In some embodiments of the invention, reference is made to conversion ofa feedstock relative to a conversion temperature T. Conversion relativeto a temperature T is defined based on the portion of the feedstock thatboils at a temperature greater than the conversion temperature T. Theamount of conversion during a process (or optionally across multipleprocesses) is defined as the weight percentage of the feedstock that isconverted from boiling at a temperature above the conversion temperatureT to boiling at a temperature below the conversion temperature T. Forexample, consider a feedstock that includes 40 wt % of components thatboils at 1050° F. (566° C.) or greater. By definition, the remaining 60wt % of the feedstock boils at less than 1050° F. (566° C.). For such afeedstock, the amount of conversion relative to a conversion temperatureof 1050° F. (566° C.) would be based only on the 40 wt % that initiallyboils at 1050° F. (566° C.) or greater. If such a feedstock is exposedto a process with 30% conversion relative to a 1050° F. (566° C.)conversion temperature, the resulting product would include 72 wt % ofcomponents boiling below 1050° F. (566° C.) and 28 wt % of componentsboiling above 1050° F. (566° C.).

In various aspects of the invention, reference may be made to one ormore types of fractions generated during distillation of a petroleumfeedstock. Such fractions may include naphtha fractions, kerosenefractions, diesel fractions, and vacuum gas oil fractions. Each of thesetypes of fractions can be defined based on a boiling range, such as aboiling range that includes at least 90 wt % of the fraction, andpreferably at least 95 wt % of the fraction. For example, for many typesof naphtha fractions, at least 90 wt % of the fraction, and preferablyat least 95 wt %, can have a boiling point in the range of 85° F. (29°C.) to 350° F. (177° C.). For some heavier naphtha fractions, at least90 wt of the fraction, and preferably at least 95 wt %, can have aboiling point in the range of 85° F. (29° C.) to 400° F. (204° C.). Fora kerosene fraction, at least 90 wt % of the fraction, and preferably atleast 95 wt %, can have a boiling point in the range of 300° F. (149°C.) to 600° F. (288° C.). Alternatively, for a kerosene fractiontargeted for some uses, such as jet fuel production, at least 90 wt % ofthe fraction, and preferably at least 95 wt %, can have a boiling pointin the range of 300° F. (149° C.) to 550° F. (288° C.). For a dieselfraction, at least 90 wt % of the fraction, and preferably at least 95wt %, can have a boiling point in the range of 400° F. (204° C.) to 750°F. (399° C.). For a vacuum gas oil fraction, at least 90 wt % of thefraction, and preferably at least 95 wt %, can have a boiling point inthe range of 650° F. (343° C.) to 1100° F. (593° C.). Optionally, forsome vacuum gas oil fractions, a narrower boiling range may bedesirable. For such vacuum gas oil fractions, at least 90 wt % of thefraction, and preferably at least 95 wt %, can have a boiling point inthe range of 650° F. (343° C.) to 1000° F. (538° C.).

Heavy Oil Feed.

In various aspects, a hydroprocessed product is produced from a heavyoil feed component. Examples of heavy oils include, but are not limitedto, heavy crude oils, distillation residues, heavy oils coming fromcatalytic treatment (such as heavy cycle oils from fluid catalyticcracking), thermal tars (such as oils from visbreaking or similarthermal processes), oils (such as bitumen) from oil sands and heavy oilsderived from coal.

Heavy oils can be liquid, semi-solid, anchor solid. Additional examplesof particular heavy oils that can be hydroprocessed, treated or upgradedaccording to this invention include Athabasca bitumen, vacuum resid fromBrazilian Santos and Campos basins, Egyptian Gulf of Suez, Chad,Venezuelan Zulia, Malaysia, and Indonesia. Sumatra. Other examples ofheavy oil include residuum from refinery distillation processes,including atmospheric and vacuum distillation processes. Such heavy oilscan have an initial ASTM D6352 boiling point of 650° F. (343° C.) orgreater. Preferably, the heavy oils will have an ASTM D6352 10%distillation point of at least 650° F. (343° C.), alternatively at least660° F. (349° C.) or at least 750° F. (399° C.) In some aspects theD6352 10% distillation point can be still greater, such as at least 950°F. (510° C.), or at least 1020° F. (549° C.), or at least 1050° F. (566°C.).

In addition to initial boiling points and/or 10% distillation points,other distillation points may also be useful in characterizing afeedstock. For example, a feedstock can be characterized based on theportion of the feedstock that boils above 1050° F. (566° C.). In someaspects, a feedstock can have an ASTM D6352 70% distillation point of1050° F. (566° C.) or greater, or a 60% distillation point of 1050° F.(566° C.) or greater, or a 50% distillation point of 1050° F. (566° C.)or greater, or a 40% distillation point of 1050° F. or greater.

Still another way of characterizing a feedstock is by characterizing theflow rate of a portion of the feed relative to the amount of catalystbeing used for processing the feed. For example, the portion of afeedstock that boils at about 1050° F. (566° C.) or above is often amore difficult portion of a feedstock to process. As a result, thepractical flow rate for a feedstock is influenced by the amount of thefeedstock that boils above 1050° F. relative to the amount ofhydroprocessing catalyst. In some aspects, the liquid hourly spacevelocity of the 1050° F. (566° C.+) portion of a combined feedstock(including both fresh feed and solvent) relative to hydroprocessingcatalyst can be at least about 0.05 hr⁻¹, such as at least about 0.10hr⁻¹, or at least about 0.12 hr⁻¹, or at least about 0.15 hr⁻¹, or atleast about 0.20 hr⁻¹.

Heavy oils can be relatively high in total acid number (TAN). TAN can beexpressed in terms of mg of KOH per g of heavy oil. For example, someheavy hydrocarbon oils that can be optionally hydroprocessed accordingto this invention have a TAN of at least 0.1, at least 0.3, or at least1.

Density, or weight per volume, of the heavy hydrocarbon can bedetermined according to ASTM D287-92 (2006) Standard Test Method for APIGravity of Crude Petroleum and Petroleum Products (Hydrometer Method),and is provided in terms of API gravity. In general, the higher the APIgravity, the less dense the oil. API gravity is at most 20° in oneaspect, at most 15° in another aspect, and at most 10° in anotheraspect.

Heavy oils can be high in metals. For example, the heavy oil can be highin total nickel, vanadium and iron contents. In one embodiment, theheavy oil will contain at least 0.00005 grams of Ni/V/Fe (50 ppm) or atleast 0.0002 grams of Ni/V/Fe (200 ppm) per gram of heavy oil, on atotal elemental basis of nickel, vanadium and iron.

Contaminants such as nitrogen and sulfur are typically found in heavyoils, often in organically-bound form. Nitrogen content can range fromabout 50 wppm to about 6000 wppm elemental nitrogen, or about 1000 wppmto about 5000 wppm elemental nitrogen, or about 200 wppm to about 3500wppm, based on total weight of the heavy hydrocarbon component. Thenitrogen containing compounds can be present as basic or non-basicnitrogen species. Examples of basic nitrogen species include quinolinesand substituted quinolines. Examples of non-basic nitrogen speciesinclude carbazoles and substituted carbazoles.

The invention is particularly suited to treating heavy oils containingat east 500 wppm elemental sulfur, based on total weight of the heavyoil. Generally, the sulfur content of such heavy oils can range fromabout 500 wppm to about 100,000 wppm elemental sulfur, or from about1000 wppm to about 60,000 wppm, or from about 5000 wppm to about 50,000wppm, based on total weight of the heavy component. In embodiments, theheavy oil feed component can contain at least 1 wt %, at least 2 wt %,or even at least 3 wt % sulfur. Sulfur will usually be present asorganically bound sulfur. Examples of such sulfur compounds include theclass of heterocyclic sulfur compounds such as thiophenes,tetrahydrothiophenes, benzothiophenes and their higher homologs andanalogs. Other organically bound sulfur compounds include aliphatic,naphthenic, and aromatic mercaptans, sulfides, di- and polysulfides.

Heavy oils can be high in n-pentane asphaltenes in some aspects, theheavy oil can contain at least about 5 wt % of n-pentane asphaltenes,such as at least about 10 wt % or at least 15 wt % n-pentaneasphaltenes.

Solvent

In various aspects of the invention, the hydroprocessing of a heavy oilfeed component is facilitated by adding a solvent component. Two typesof solvent components are contemplated in various aspects. One type ofsolvent component is a solvent component that contains at least onesingle-ring aromatic ring compound, and more preferably more than onesingle-ring aromatic ring compound. The solvent is also a low boilingsolvent relative to the heavy hydrocarbon oil. By the term “single-ringaromatic compound” as used herein, it is defined as a hydrocarboncompound containing only one cyclic ring wherein the cyclic ring isaromatic in nature.

For a solvent component containing at least one single-ring aromaticcompound, the solvent preferably has an ASTM D86 90% distillation pointof less than 300° C. (572° F.). Alternatively, the solvent has an ASTMD86 90% distillation point of less than 250° C. (482° F.) or less than200° C. (392° F.). Additionally or alternately, the solvent can have anASTM D86 10% distillation point of at least 120° C. (248° F.), such asat least 140° C. (284° F.) or at least 150° C. (302° F.

The single-ring aromatic compound or compounds in particular haverelatively low boiling points compared to the heavy hydrocarbon oil.Preferably, none of the single-ring aromatic compounds of the solventhas a boiling point of greater than 550° F. (288° C.), or greater than500° F. (260° C.), or greater than 450° F. (232° C.), or greater than400° F. (204° C.).

The single-ring aromatic can include one or more hydrocarbonsubstituents, such as from 1 to 3 or 1 to 2 hydrocarbon substituents.Such substituents can be any hydrocarbon group that is consistent withthe overall solvent distillation characteristics. Examples of suchhydrocarbon groups include, but are not limited to, those selected fromthe group consisting of C₁-C₆ alkyl and C₁-C₆ alkenyl, wherein thehydrocarbon groups can be branched or linear and the hydrocarbon groupscan be the same or different. A particular example of such a sink-ringaromatic that includes one or more hydrocarbon substituents istrimethylbenzene (TMB).

The solvent preferably contains sufficient single-ring aromaticcomponent(s) to effectively increase run length during hydroprocessing.For example, the solvent can be comprised of about 20 wt % to about 80wt % of the single ring aromatic component, such as at least 50 wt % ofthe single-ring aromatic component, or at least 60 wt %, or at least 70wt %, based on total weight of the solvent component.

The density of the solvent component can also be determined according toASTM D287-92 (2006) Standard Test Method for API Gravity of CrudePetroleum and Petroleum Products (Hydrometer Method) in terms of APIgravity, API gravity of the solvent component is at most 35° in oneaspect, at most 30° in another aspect, and at most 25° in anotheraspect.

In other aspects of the invention, the solvent component can correspondto a recycle stream of a portion of the liquid effluent or productgenerated from the hydroprocessing reaction. The recycle stream can be aportion of the total liquid effluent, or the recycle stream can includea portion of one or more distillation fractions of the liquid productfrom hydroprocessing. An example of a recycle stream corresponding to aportion of a distillation fraction is a recycle stream corresponding toa portion of the distillate boiling range product from hydroprocessingof the heavy feed.

Recycling a portion of the total liquid effluent for use as a solventprovides a variety of advantages. Because the recycled portion is a partof the total liquid effluent, a separation does not have to be performedto recover the solvent after hydroprocessing. Instead, the outputeffluent from hydroprocessing can simply be divided to form a productstream and a recycle stream. In some embodiments, fractionation of thetotal liquid product may not occur until after additional processing isperformed, such as additional hydroprocessing to remove contaminants orimprove cold flow properties. Recycling a portion of the total liquideffluent means that fully hydroprocessed products are not recycled to anearly stage, which can increase the available processing volume forlater hydroprocessing stages.

Optionally, other portions of the hydroprocessed product may be recycledin addition to the portion of the total liquid effluent. For example,after withdrawing the recycle stream portion of the total liquideffluent, the remaining portion of the total liquid effluent may beseparated or fractionated to form various fractions, such as one or morenaphtha fractions, one or more kerosene and/or distillate fractions, oneor more atmospheric or vacuum gas oil fractions, and a bottoms or residfraction. A portion of one or more of these product fractions can alsobe recycled for use as part of the combined hydroprocessing feed. Forexample, a portion of a kerosene product fraction or distillate productfraction can be recycled and combined with the heavy oil feed and therecycled portion of the total liquid effluent to form thehydroprocessing feed. These recycled product fractions, based on recycleof one or more fractions that have a narrower boiling range than thetotal liquid product, can correspond to at least about 2 wt % of thecombined hydroprocessing feed, such as at least about 5 wt % or at leastabout 10 wt %. Such recycled product fractions can correspond to about50 wt % or less of the combined hydroprocessing feed, and preferablyabout 25 wt % of the combined hydroprocessing feed or less, such asabout 15 wt % or less or 10 wt % or less.

One potential concern with using a product fraction as a recycle streamis the possibility of further conversion of the recycled productfraction during hydroprocessing. For example, a product fraction where90 wt % of the product fraction boils in a boiling range of 300° F.(149° C.) to 600° F. (316° C.) corresponds to a kerosene fraction.Further conversion of this product fraction when used as a recyclesolvent would result in formation of additional components with boilingpoints less than 300° F. (149° C.). Such low boiling point componentscorrespond to either naphtha or light ends, which are lower valuefractions. Preferably, less than 10 wt % of a product fraction isconverted to components with a boiling point below the boiling range ofthe product fraction when exposed to the hydroprocessing environment asa recycle solvent, and more preferably less than 5 wt % of a recycledproduct fraction undergoes conversion.

In an alternative aspect of the invention, the total liquid effluentfrom the hydroprocessing reaction can be fractionated, so that the onlyrecycle inputs to the hydroprocessing feed are recycled portions fromthe product fractions. In this type of aspect, the amount of recycledproduct fractions can correspond to at least about 10 wt % of thehydroprocessing feed, such as at least about 20 wt %. The amount ofrecycled product fractions can correspond to about 50 wt % or less, suchas about 30 wt % or less. Suitable product fractions for recycle includekerosene fractions, distillate (including diesel) fractions, gas oilfractions (including atmospheric and vacuum gas oils), and combinationsthereof.

The solvent component should be combined with the heavy hydrocarbon oilcomponent to effectively increase run length during hydroprocessing. Forexample, the solvent and heavy hydrocarbon component can be combined soas to produce a combined feedstock that is comprised of from 10 wt % to90 wt % of the heavy hydrocarbon oil component and from 10 wt % to 90 wt% of the solvent component, based on total weight of the combined feed.Alternatively, the solvent and heavy hydrocarbon component are combinedso as to produce a combined feedstock that is comprised of from 30 wt %to 80 wt % of the heavy hydrocarbon oil component and from 20 wt % to 70wt % of the solvent component, based on total weight of the combinedfeed. In some aspects, the solvent component is about 50 wt % or less ofthe combined feedstock, such as about 40 wt % or less or about 30 wt %or less. In other aspects where at least a portion of the solventcomponent corresponds to a recycled portion of the total liquideffluent, the solvent component can be greater than 50 wt % of thecombined feedstock.

Another way of characterizing an amount of feedstock relative to anamount of solvent component, such as a recycle component, is as a ratioof solvent component to feedstock. For example, the ratio of solventcomponent to feedstock on a weight basis can be at least about 0.2, suchas from about 0.3 to about 6.0, and preferably at least about 0.5 and/orless than about 5.0 or less than about 3.0.

The solvent can be combined with the heavy hydrocarbon oil within thehydroprocessing vessel or hydroprocessing zone. Alternatively, thesolvent and heavy hydrocarbon oil can be supplied as separate streamsand combined into one feed stream prior to entering the hydroprocessingvessel or hydroprocessing zone.

In still another option, instead of feeding a solvent componentcorresponding to a recycled portion of the total liquid effluent into areactor from the reactor inlet, part of the solvent may be fed to thereactor via interbed quench zones. This would allow the solvent to helpcontrol reaction exothermicity (adiabatic temperature rise) and improvethe liquid flow distribution in the reactor bed.

Hydroprocessing Catalysts

The catalysts used for hydroconversion of a heavy oil feed can includeconventional hydroprocessing catalysts, such as those that comprise atleast one Group VIII non-noble metal (Columns 8-10 of IUPAC periodictable), preferably Fe, Co, and/or Ni, such as Co and/or Ni; and at leastone Group VI metal (Column 6 of IUPAC periodic table), preferably Moand/or W. Such hydroprocessing catalysts optionally include transitionmetal sulfides that are impregnated or dispersed on a refractory supportor carrier such as alumina and/or silica. The support or carrier itselftypically has no significant/measurable catalytic activity.Substantially carrier- or support-free catalysts, commonly referred toas bulk catalysts, generally have higher volumetric activities thantheir supported counterparts.

The catalysts can either be in bulk form or in supported form. Inpreferred embodiments, the catalyst is, or is comprised of a bulk metalcatalyst. In addition to alumina and/or silica, other suitablesupport/carrier materials can include, but are not limited to, zeolites,titania, silica-titania, and titania-alumina. It is within the scope ofthe invention that more than one type of hydroprocessing catalyst can beused in one or multiple reaction vessels.

The at least one Group VIII non-noble metal, in oxide form, cantypically be present in an amount ranging from about 2 wt % to about 30wt %, preferably from about 4 wt % to about 15 wt %. The at least oneGroup VI metal, in oxide form, can typically be present in an amountranging from about 2 wt % to about 60 wt %, preferably from about 6 wt %to about 40 wt % or from about 10 wt % to about 30 wt %. These weightpercents are based on the total weight of the catalyst. It is noted thatunder hydroprocessing conditions, the metals may be present as metalsulfides and/or may be converted metal sulfides prior to performinghydroprocessing on an intended feed.

A vessel or hydroprocessing zone in which catalytic activity occurs caninclude one or more hydroprocessing catalysts. Such catalysts can bemixed or stacked, with the catalyst preferably being in a fixed bed inthe vessel or hydroprocessing zone.

The support can be impregnated with the desired metals to form thehydroprocessing catalyst. In particular impregnation embodiments, thesupport is heat treated at temperatures in a range of from 400° C. to1200° C. (752° F. to 2192° F.), or from 450° C. to 1000° C. (842° F. to1832° F.), or from 600° C. to 900° C. (1112° F. to 1652° F.), prior toimpregnation with the metals.

In an alternative embodiment, the hydroprocessing catalyst is comprisedof shaped extrudates. The extrudate diameters range from 1/32nd to⅛^(th) inch, from 1/20^(th) to 1/10^(th) inch, or from 1/20^(th) to1/16^(th) inch. The extrudates can be cylindrical or shaped.Non-limiting examples of extrudate shapes include trilobes andquadralobes.

The process of this invention can be effectively carried out using ahydroprocessing catalyst having a median pore diameter of at least 85 Å,such as at least 90 Å, and a median pore diameter of 120 Å or less, suchas 1.05 Å or less. This can correspond, for example, to a catalyst witha median pore diameter from 85 Å to 120 Å, such as from 85 Å to 100 Å orfrom 85 Å to 98 Å. Pore diameter is preferably determined according toASTM Method D4284-07 Mercury Porosimetry.

It is preferred that the hydroprocessing catalyst have a pore sizedistribution that is not so great as to negatively impact catalystactivity or selectivity. For example, the hydroprocessing catalyst canhave a pore size distribution in which at least 60% of the pores have apore diameter within 45 Å, 35 Å, or 25 Å of the median pore diameter. Incertain embodiments, the catalyst has a median pore diameter in a rangeof from 85 Å to 120 Å, with at least 60% of the pores having a porediameter within 45 Å, 35 Å, or 25 Å of the median pore diameter.

Pore volume should be sufficiently large to further contribute tocatalyst activity or selectivity. For example, the hydroprocessingcatalyst can have a pore volume of at least 0.3 cm³/g, at least 0.7cm³/g, or at least 0.9 cm³/g. In certain embodiments, pore volume canrange from 0.3-0.99 cm³/g, 0.4-0.8 cm³/g, or 0.5-0.7 cm³/g.

In certain aspects, the catalyst exists in shaped forms, for example,pellets, cylinders, and/or extrudates. The catalyst typically has a flatplate crush strength in a range of from 50-500 N/cm, or 60-400 N/cm, or100-350 N/cm, or 200-300 N/cm, or 220-280 N/cm.

In some aspects, a combination of catalysts can be used forhydroprocessing of a heavy oil feed. For example, a heavy oil feed canbe contacted first by a demetaliation catalyst, such as a catalystincluding NiMo or CoMo on a support with a median pore diameter of 150 Åor greater, such as 200 Å or greater. A demetallation catalystrepresents a lower activity catalyst that is effective for removing atleast a portion of the metals content of a feed. This allows a lessexpensive catalyst to be used to remove a portion of the metals, thusextending the lifetime of any subsequent higher activity catalysts. Thedemetallized effluent from the demetallation process can then becontacted with a catalyst having a median pore diameter of 85 Å to 120Å.

Processing Conditions

Hydroprocessing (alternatively hydroconversion) generally refers totreating or upgrading the heavy hydrocarbon oil component that contactsthe hydroprocessing catalyst. Hydroprocessing particularly refers to anyprocess that is carried out in the presence of hydrogen, including, butnot limited to, hydroconversion, hydrocracking (which includes selectivehydrocracking), hydrogenation, hydrotreating, hydrodesulfurization,hydrodenitrogenation, hydrodemetailation, hydrodearomatization,hydroisomerization, and hydrodewaxing including selective hydrocracking.The hydroprocessing reaction is carried out in a vessel or ahydroprocessing zone in which heavy hydrocarbon and solvent contact thehydroprocessing catalyst in the presence of hydrogen.

Contacting conditions in the contacting or hydroprocessing zone caninclude, but are not limited to, temperature, pressure, hydrogen flow,hydrocarbon feed flow, or combinations thereof. Contacting conditions insome embodiments are controlled to yield a product with specificproperties.

Hydroprocessing is carried out in the presence of hydrogen. A hydrogenstream is, therefore, fed or injected into a vessel or reaction zone orhydroprocessing zone in which the hydroprocessing catalyst is located.Hydrogen, which is contained in a hydrogen “treat gas,” is provided tothe reaction zone. Treat gas, as referred to herein, can be either purehydrogen or a hydrogen-containing gas, which is a gas stream containinghydrogen in an amount that is sufficient for the intended reaction(s),optionally including one or more other gasses (e.g., nitrogen and lighthydrocarbons such as methane), and which will not adversely interferewith or affect either the reactions or the products. Impurities, such asH₂S and NH₃ are undesirable and would typically be removed from thetreat gas before it is conducted to the reactor. The treat gas streamintroduced into a reaction stage will preferably contain at least about50 vol % and more preferably at least about 75 vol % hydrogen.

Hydrogen can be supplied at a rate of from 1000 SCF/B (standard cubicfeet of hydrogen per barrel of total feed) (178 S m³/m³) to 10000 SCF/B(1780 S m³/m³). Preferably, the hydrogen is provided in a range of from2000 SCF/B (356 S m³/m³) to 5000 SCF/B (891 S m/m³).

Hydrogen can be supplied co-currently with the heavy hydrocarbon oiland/or solvent or separately via a separate gas conduit to thehydroprocessing zone. The contact of the heavy hydrocarbon oil andsolvent with the hydroprocessing catalyst and the hydrogen produces atotal product that includes a hydroprocessed oil product, and, in someembodiments, gas.

The temperature in the contacting zone can be at least about 680° F.(360° C.), such as at least about 700° F. (371° C.), and preferably atleast about 716° F. (380° C.), such as at least about 750° F. (399° C.)or at least about 788° F. (420° C.). Additionally or alternately, thetemperature in the contacting zone can be about 950° F. (510° C.) orless, such as about 900° F. (482° C.) or less, and preferably about 869°F. (465° C.) or less or about 842° F. (450° C.) or less.

Total pressure in the contacting zone can range from 200 psig (1379kPa-g) to 3000 psig (20684 kPa-g), such as from 400 psig (2758 kPa-g) to2000 psig (13790 kPa-g), or from 650 psig (4482 kPa-g) to 1500 psig(10342 kPa-g), or from 650 psig (4482 kPa-g) to 1200 psig (8273 kPa-g).Preferably, a heavy oil can be hydroprocessed under low hydrogen partialpressure conditions. In such aspects, the hydrogen partial pressureduring hydroprocessing can be from about 200 psia (1379 kPa) to about1000 psia (6895 kPa), such as from 500 psia (3447 kPa) to about 800 psia(5516 kPa). Additionally or alternately, the hydrogen partial pressurecan be at least about 200 psia (1379 kPa), or at least about 400 psia(2758 kPa), or at least about 600 psia (4137 kPa). Additionally oralternately, the hydrogen partial pressure can be about 1000 psia (6895kPa) or less, such as about 900 psia (6205 kPa) or less, or about 850psia (5861 kPa) or less, or about 800 psia (5516 kPa) or less, or about750 psia (5171 kPa) or less. In such aspects with low hydrogen partialpressure, the total pressure in the reactor can be about 1200 psig (8274kPa-g) or less, and preferably 1000 psig (6895 kPa-g) or less, such asabout 900 psig (6205 kPa-g) or less or about 800 psig (5516 kPa-g) orless.

Liquid hourly space velocity (LHSV) of the combined heavy hydrocarbonoil and recycle components will generally range from 0.1 to 30 h⁻¹, or0.4 h⁻¹ to 20 h⁻¹, or 0.5 to 10 h⁻¹. In some aspects, LHSV is at least15 h⁻¹, or at least 10 h⁻¹, or at least 5 h⁻¹. Alternatively, in someaspects LHSV is about 2.0 h⁻¹ or less, or about 1.5 h⁻¹ or less, orabout 1.0 h⁻¹ or less.

Based on the reaction conditions described above, in various aspects ofthe invention, a portion of the reactions taking place in thehydroprocessing reaction environment can correspond to thermal crackingreactions. In addition to the reactions expected during hydroprocessingof a feed in the presence of hydrogen and a hydroprocessing catalyst,thermal cracking reactions can also occur at temperatures of 360° C. andgreater. In the hydroprocessing reaction environment, the presence ofhydrogen and catalyst can reduce the likelihood of coke formation basedon radicals formed during thermal cracking.

In an embodiment of the invention, contacting the input feed to thehydroconversion reactor with the hydroprocessing catalyst in thepresence of hydrogen to produce a hydroprocessed product is carried outin a single contacting zone. In another aspect, contacting is carriedout in two or more contacting zones.

In various embodiments of the invention, the combination of processingconditions can be selected to achieve a desired level of conversion of afeedstock. For various types of heavy oil feedstocks, conversionrelative to a conversion temperature of 1050° F. (566° C.) is aconvenient way to characterize the amount of feedstock conversion. Forexample, the process conditions can be selected to achieve at leastabout 25% conversion of the 1050° F. portion of a feedstock. In otherwords, the conditions are selected so that at least about 25 wt % of theportion of the feed that boils above 1050° F. (566° C.) is converted toa portion that boils below 1050° F. (566° C.). In some aspects, theamount of conversion relative to 1050° F. (566° C.) can be at leastabout 40%, such as at least about 50% or at least about 60%.Additionally or alternately the conversion percentage can be about 80%or less, such as about 75% or less or about 70% or less. An example of asuitable amount of conversion can be a conversion percentage from about40% to about 80%, such as about 50% to about 70%.

In other embodiments of the invention, a greater amount of conversionmay be desirable. For example, in order to segregate molecules with lowhydrogen to carbon ratios using hydroprocessing, a conversion percentageof at least about 80% can be desirable, such as at least about 85%, orat least about 90%. Additionally or alternately, the conversionpercentage can be about 95% or less, such as about 90% or less. Theselevels of conversion can also be useful, for example, for concentratingwax in the 650° F.+ (343° C.+) or 700° F.+ (371° C.+) portion of afeedstock, or for forming a low sulfur fuel oil. Optionally, a feedstockwith a sulfur content of about 3.0 wt % or less can be used when thesehigher levels of conversion are desired.

Hydroprocessed Product

Relative to the heavy oil feed component in the feedstream, thehydroprocessed product will be a material or crude product that exhibitsreductions in such properties as average molecular weight, boiling pointrange, density and/or concentration of sulfur, nitrogen, oxygen, andmetals.

In an embodiment of the invention, contacting the heavy oil feedcomponent and recycle or other solvent component with thehydroprocessing catalyst in the presence of hydrogen to produce ahydroprocessed product is carried out in a single contacting zone. Inanother embodiment, contacting is carried out in two or more contactingzones. The total hydroprocessed product can be separated to form one ormore particularly desired liquid products and one or more gas products.

In some embodiments of the invention, the liquid product is blended witha hydrocarbon feedstock that is the same as or different from the heavyoil feed component. For example, the liquid hydroprocessed product canbe combined with a hydrocarbon oil having a different viscosity,resulting in a blended product having a viscosity that is between theviscosity of the liquid hydroprocessed product and the viscosity of theheavy oil feed component.

In some embodiments of the invention, the hydroprocessed product and/orthe blended product are transported to a refinery and distilled toproduce one or more distillate fractions. The distillate fractions canbe catalytically processed to produce commercial products such astransportation fuel, lubricants, or chemicals. A bottoms fraction canalso be produced, such as bottoms fraction with an ASTM D6352 10%distillation point of at least about 600° F. (316° C.), or an ASTM D635210% distillation point of at least about 650° F. (343° C.), or a bottomsfraction with a still higher 10% distillation point, such as at leastabout 750° F. (399° C.) or at least about 800° F. (427° C.).

In some embodiments of the invention, the hydroprocessed product has atotal Ni/V/Fe content of at most 50%, or at most 30%, or at most 10%, orat most 5%, or at most 1% of the total Ni/V/Fe content (by wt %) of theheavy oil feed component. In certain embodiments, the fraction of thehydroprocessed product that has an ASTM D6352 10% distillation point ofat least about 650° F. (343° C.) and higher (i.e., 650° F.+ productfraction) has, per gram of 650° F.+ (343° C.+) product fraction, a totalNi/V/Fe content in a range of from 1×10⁻⁷ grams to 2×10⁻⁴ grams (0.1 to200 ppm), or 3×10⁻⁷ grams to 1×10⁻⁴ grams (0.3 to 100 ppm), or 1×10⁻⁶grams to 1×10⁻⁴ grams (1 to 100 ppm). In certain embodiments, the 650°F. + (343° C.+) product fraction has not greater than 4×10⁻⁵ grams ofNi/V/Fe (40 ppm).

In certain embodiments of the invention, the hydroprocessed product hasan API gravity that is 100-160%, or 110-140% of that of the heavy oilfeed component. In certain embodiments, API gravity of thehydroprocessed product is from 10°-40°, or 12°-35°, or 14°-30°.

In certain embodiments of the invention, the hydroprocessed product hasa viscosity of at most 90%, or at most 80%, or at most 70% of that ofthe heavy oil feed component. In some embodiments, the viscosity of thehydroprocessed product is at most 90% of the viscosity of the heavy oilfeed component, white the API gravity of the hydroprocessed product is100-160%, or 105-155%, or 110-150% of that of the heavy oil feedcomponent.

In an alternative embodiment, the 650° F.+ (343° C.+) product fractioncan have a viscosity at 100° C. of 10 to 150 cst, or 15 to 120 cst, or20 to 100 est. Most atmospheric resids of crude oils range from 40 to200 cst. In certain embodiments, 650° F.+ (343° C.+) product fractionhas a viscosity of at most 90%, or at most 50%, or at most 5% of that ofthe heavy oil feed component.

In some embodiments of the invention, the hydroprocessed product has atotal heteroatom (i.e., S/N/O) content of at most 50%, or at most 25%,or at most 10%, or at most 5% of the total heteroatom content of theheavy oil feed component.

In some embodiments of the invention, the sulfur content of thehydroprocessed product is at most 50%, or at most 10%, or at most 5% ofthe sulfur content (by wt %) of the heavy oil feed component. The totalnitrogen content of the hydroprocessed product is at most 85%, or atmost 50%, or at most 25% of the total nitrogen (by wt %) of the heavyoil feed component.

In still other embodiments of the invention, the 650° F.+ (343° C.+)product fraction can have an increased content of waxy moleculesrelative to the wax content of the feedstock. Under hydroprocessingconditions including a temperature of at least about 420° C., such as atleast about 440° C., and a partial pressure of hydrogen of less thanabout 1000 psia (6.9 MPa) and/or a total pressure of less than about1000 psig (6.9 MPag), alkylaromatic molecules with boiling points in thevacuum gas oil range (>650° F. or 343° C.) are selectively cracked toform 650° F.+ (343° C.+) aliphatic (and preferably paraffinic) moleculesand aromatics. Prior to hydroprocessing, these molecules would not beclassified as waxy molecules due to the aromatic portions of themolecules. After hydroprocessing, the 650° F.+ (343° C.+) productfraction can be enriched in waxy molecules due to the formation ofdistinct aliphatic and aromatic molecules based on the high boilingaromatic molecules. Preferably, when formation of a product fractionenriched in waxy molecules is desired, the feedstock to thehydroprocessing reaction can have an ASTM D6352 10% distillation pointof at least about 900° F. (482° C.), and more preferably at least about950° F. Using a feedstock with a reduced amount of lower boilingmaterial is helpful for subsequent separation of wax from thehydroprocessed effluent. In some embodiments, the bottoms fraction usedfor wax recovery can correspond to a higher boiling fraction, such as a750° F.+ (399° C.+) bottoms fraction, or an 800° F.+ (427° C.+) bottomsfraction.

The selective production in the process of the invention of 650° F.+(343° C.+) wax and 650° F.+ (343° C.+) polynuclear aromatics with shortside chains from atmospheric and vacuum resids of crude oil isunexpected based in part on the unusual reaction conditions. At theseconditions, the preferred reaction pathway thr alkylaromatics is thermalcracking, while hydrogenation of alkylaromatics to saturated, vacuum gasoil boiling range liquids is suppressed. This is unexpected, becausethermal cracking is generally believed to have poor selectivity. Theexpected result under thermal cracking conditions is for alkylaromatics,alkylnaphthenes, paraffins, and isoparaffins in the vacuum gas oilboiling range to all crack, resulting in production of C₄−, naphtha, anddistillate boiling range molecules at similar rates from all of thevarious initial molecules. Instead, it has been discoveredalkylaromatics thermally crack much faster than paraffins andisoparaffins, enabling the production of a vacuum gas oil saturatesfraction that is highly enriched in wax. This result has not beenpreviously found in part due to the rapid coking that occurs duringhydroprocessing of vacuum gas oil, atmospheric resid, and/or vacuumresid fractions under conventional conditions. Fouling andincompatibility hinders operation of waxy vacuum gas oils and residseven in slurry phase and ebullating bed hydrocrackers. Furthermore,slurry and ebullating beds operate in the bulk liquid phase, and areknown to have poor thermal cracking selectivity because of liquid phasemass transport limitations. Additionally, the result cannot be observedat partial pressures of hydrogen greater than 1000 psia (6.9 MPa), dueto the shift in the equilibrium toward increased hydrogenation ofaromatics at higher pressures.

In addition to allowing for production of wax from high boilingalkylaromatic compounds, the reaction conditions also assist inproducing a higher purity wax product. Due to the low hydrogen partialpressure used for thermally cracking the alkylaromatic compounds to formwax, an increased percentage of the resulting aromatic compounds are notsaturated or otherwise hydrogenated. By allowing the aromatic compoundsto retain their aromaticity, the aromatic compounds can subsequently beremoved from the wax product by a conventional method, such as solventextraction. Using a higher (conventional) partial pressure of hydrogenof more than 1000 psia (6.9 MPa), more of the aromatic compounds wouldbe saturated, resulting in naphthenes that cannot be as readilyseparated using solvent extraction.

In some embodiments, processes according to the invention can also beused for production of low sulfur fuel oil, such as a fuel oil with asulfur content of about 1 wt % or less. The higher severityhydroprocessing conditions suitable for wax concentration, such as atemperature of at least about 420° C., preferably at least about 440°C., are also suitable for increasing the percentage of sulfur removalfrom a feed. Under reaction conditions suitable for at least about 80%conversion of the 1050° F.+ (566° C.+) portion of the feed, andpreferably at least about 90% conversion, an 800° F.+ (427° C.+) bottomsproduct can be generated with a sulfur concentration of less than 1 wt%. This 800° F.+ (427° C.+) bottoms product is suitable for use as a lowsulfur fuel oil. Such hydroprocessing conditions are also suitable forat least 75% desulfurization of the feedstock, such as at least about80% desulfurization or at least about 90% desulfurization. For example,for a feed having an initial concentration of about 4 wt %, at least 75%desulfurization is required to achieve a low sulfur fuel oil with asulfur concentration of about 1 wt % or less. Such levels ofdesulfurization can be achieved by using conditions severe enough toproduce at least 80% conversion of a feed based on a 1050° F. (566° C.)conversion temperature, such as at least 90% conversion. Optionally, thefeed used for forming the low sulfur fuel oil can be a feed with ahigher boiling range, such as a feed with an ASTM D6352 10% distillationpoint of at least about 900° F. (482° C.), and more preferably at leastabout 950° F. (510° C.).

If it is desirable to generate a wax from the 800° F.+ (427° C.+)product generated by hydroprocessing of a feed, the wax in the 800° F.+(427° C.+) product can be separated out. The remaining portion of the800° F.+ (427° C.+) product can then be used as a low sulfur fuel oil.In an alternative embodiment, an initial feed can be used that has a lowinitial wax content and/or separation of wax from the 800° F.+ (427°C.+) product may not be desired. In such an alternative embodiment, the800° F.+ (427° C.+) product can be used as a low sulfur fuel oil withoutprior removal or separation of wax.

Example of Processing Configuration

FIG. 1 schematically shows an example of a configuration suitable forhydroprocessing a heavy oil feedstock. In FIG. 1, a feedstock 105comprising at least a portion of a heavy oil teed component is passedinto a hydroprocessing reaction zone 110. A hydrogen stream 107 is alsointroduced into the hydroprocessing reaction zone 110. Hydrogen stream107 is shown as being introduced separately into reaction zone 110, buthydrogen stream 107 can also be mixed with feedstock 105 prior toentering reaction zone 110. In the configuration shown in FIG. 1,feedstock 105 is mixed with a recycle portion 122 of the liquid effluentthat has been separated from the hydroprocessing reaction zone effluent,prior to the mixture entering the hydroprocessing reaction zone 105.Alternatively, the recycle portion 122 can be mixed with feedstock 105in the hydroprocessing reaction zone 110. As still another alternative,a separate solvent can be added in place of or in addition to recycleportion 122.

Preferably hydroprocessing reaction zone 110 can be operated to achievea desired level of conversion, such as a desired level of conversionrelative to a 1050° F. (566° C.) conversion temperature. The effluent115 from reaction zone 105 is passed into a separator 120, such as ahigh pressure separator. The separator 120 can separate a gas phaseportion of effluent 115 from a liquid phase portion of the effluent. Thegas phase portion of effluent 115 can optionally include a portion ofmolecules that would typically be considered as part of the naphthaboiling range. In the configuration shown in FIG. 1, the liquid phaseportion is then split into recycle portion 122 and a product portion128.

In the configuration shown in FIG. 1, the product portion 128 of theliquid effluent from hydroprocessing reactor 110 is separated in anatmospheric distillation tower 130 or another type of separator suitablefor performing a comparable fractionation. The atmospheric distillationunit 130 fractionates product portion 128 to form at least a distillateproduct portion 135 and a bottoms portion 133. Optionally, a naphthaboiling range portion (not shown) can also be produced, if naphthaboiling range molecules are still present in product portion 128.Optionally, more than one distillate boiling range fraction can begenerated, such as a kerosene portion and a diesel portion.

The bottoms portion 133 is then passed into a vacuum distillation unit140 or another comparable type of separator that performs afractionation in an environment with a reduced pressure (i.e., apressure that is less than atmospheric). The vacuum distillation unit140 forms at least one vacuum gas oil portion 145 and a vacuum bottomsportion 143. The vacuum gas oil portion 145 can be suitable for furtherprocessing, such as additional hydroprocessing or other processing toform fuels or lubricants, or as a feed a fluid catalytic cracker. Thebottoms portion can be used for forming fuel oils, asphalts, or othertypes of high boiling products.

In an alternative configuration, the bottoms 133 from atmosphericdistillation unit 130 can be used as a product without separation in avacuum distillation unit 140. For example, the bottoms 133 can be usedas a feed for a wax production plant.

Deasphalting of Hydroconverted Effluent

The configuration shown in FIG. 1 is an example of a configuration wherehydroprocessing is performed on a heavy oil feedstock, followed byseparation of product fractions for further use. One alternative to thetype of configuration shown in FIG. 1 is to include solvent deasphaltingof at least a portion of the hydroprocessed effluent. Solventdeasphalting allows for separation of asphaltenes from a remainingportion of a feed. Asphaltenes are typically molecules that requiresubstantial addition of hydrogen in order to make a molecule suitablefor use as a fuel. Solvent deasphalting allows these lower valuemolecules to be separated out on a basis other than boiling point, sothat higher value molecules with similar boiling points, such asmolecules with similar boiling points but higher hydrogen content, canbe retained as part of the feedstock.

Solvent deasphalting is a solvent extraction process. Suitable solventsinclude alkanes or other hydrocarbons containing about 3 to about 6carbons per molecule. Examples of suitable solvents include propane,n-butane, isobutene, and n-pentane. Alternatively, other types ofsolvents may also be suitable, such as supercritical fluids. Duringsolvent deasphalting, a feed portion is mixed with the solvent. Portionsof the feed that are soluble in the solvent are then extracted, leavingbehind a residue with little or no solubility in the solvent. Preferredsolvent deasphalting conditions for processes of the invention includemixing a feedstock fraction with a solvent in a weight ratio of fromabout 1:2 to about 1:10, such as about 1:8 or less. Preferred solventdeasphalting temperatures for processes of the invention range fromabout 40° C. to about 200° C. The pressure during solvent deasphaltingcan be from about 50 psig (345 kPag) to about 500 psig (3447 kPag).

The portion of the feedstock that is extracted with the solvent is oftenreferred to as deasphalted oil. In various embodiments of the invention,solvent deasphalting can be performed on the bottoms from atmosphericdistillation or on a portion of the bottoms from atmosphericdistillation. For example, the bottoms from vacuum distillationrepresents a portion of the atmospheric distillation bottoms that can beused as the feed to the solvent deasphalter. A portion of vacuum gas oilcan also be used as a feed to a solvent deasphalting process, eitheralone or in combination with at least a portion of vacuum distillationbottoms.

The yield of deasphalted oil from the solvent extraction process variesdepending on a variety of factors, including the nature of thefeedstock, the type of solvent, and the solvent extraction conditions. Alighter molecular weight solvent such as propane will result in a loweryield of deasphalted oil as compared to n-pentane, as fewer componentsof the heavy oil will be soluble in the shorter chain alkane. However,the deasphalted oil resulting from propane deasphalting is typically ofhigher quality, resulting in expanded options for use of the deasphaltedoil. Under preferred deasphalting conditions, increasing the temperaturewill also usually reduce the yield while increasing the quality of theresulting deasphalted oil. In various embodiments of the presentinvention, the yield of deasphalted oil from solvent deasphalting can beabout 85 wt % or less of the feed to the deasphalting process, or about75 wt % or less. In other embodiments, solvent deasphalting conditionsare selected so that the yield of deasphalted oil is at least about 25wt %, such as at least about 45 wt % or at least about 70 wt %.

After the deasphalting process, the yield of deasphalting residue can beat least about 15 wt % of the feed to the deasphalting process. Theyield of deasphalting residue is preferably up to about 75 wt % or less,but is preferably about 35 wt % or less, such as about 30 wt % or lessor 25 wt % or less. The deasphalting residue can be used, for example,for making various grades of asphalt. A deasphalting residue issometimes referred to using the number of carbons in the solvent usedfor deasphalting. For example, a solvent deasphalting process usingn-pentane will produce a deasphalted oil and a C₅ deasphalting residue.

In some aspects of the invention, solvent deasphalting can be used tosegregate molecules with lower hydrogen content. This can allow thehydroprocessing reaction to be performed under less severe conditions,so that segregation of lower hydrogen content molecules from higherhydrogen content molecules is based on solubility rather than based onboiling point. Segregating molecules with lower hydrogen content isbeneficial for several reasons. First, such lower hydrogen contentmolecules require the greatest hydrogen consumption in order to convertthe molecules to a more desirable product, such as a fuel or lubricantbase oil. Additionally, such lower hydrogen content molecules tend tohave poor properties, such as unfavorable flow properties and/or highlevels of contaminants. Thus, one of the goals of processing a feedstockis to either separate such low hydrogen content molecules out from thehigher value molecules, or to add enough hydrogen to the low hydrogencontent molecules to increase the value of the initially low hydrogencontent molecules. From a resource standpoint, separation of the lowhydrogen content molecules would be preferable, in order to reduce theseverity of reaction conditions as well as to avoid excessive hydrogenconsumption. Combining hydroprocessing with solvent deasphalting for useof such lower severity conditions while still effectively separating outlow hydrogen content molecules.

For example, using only hydroprocessing, conditions sufficient toachieve a conversion percentage of at least about 80 wt % of the 1050°F. (566° C.) portion of the feed, such as at least about 85 wt %, arerequired to effectively segregate lower hydrogen content moleculeswithin a heavy oil feed. By contrast, using a combination of solventdeasphalting and hydroprocessing, the hydroprocessing conditions can beselected to achieve a conversion of only 50% to 70% of the 1050° F.+(566° C.+) portion of the feed. This is a significantly less severelevel of conversion. The effluent from hydroprocessing is then solventdeasphalted. The deasphalting residue can have a similar hydrogencontent profile as the unconverted portion from the more severehydroprocessing conditions.

Additional Examples of Process Configurations

FIGS. 2-4 show various embodiments of processing configurations of thepresent invention that include a solvent deasphalting step fordeasphalting at least a portion of the effluent from hydroprocessing.For example, FIG. 2 shows a configuration where solvent deasphalting isperformed on the bottoms from a fractionator that performs separationsin a reduced pressure environment such as a vacuum distillation unit).Instead of using the entire reduced pressure fractionation bottoms as afuel oil product, performing solvent deasphalting can allow the reducedpressure fractionation bottoms to be separated into a deasphalted oilportion suitable for use as a heavy vacuum gas oil and a residualasphalt portion.

In the configuration shown in FIG. 2, many of the elements of theconfiguration are similar to FIG. 1. In the embodiment shown in FIG. 2,the bottoms fraction 143 from the vacuum distillation unit is passedinto a solvent deasphalting unit 250. The solvent deasphalting unit 250generates a deasphalted oil product 255 and a deasphalting residue orasphalt product 253. The deasphalted oil product 255 can be recycled forfurther hydroprocessing in hydroprocessing unit 110, subject to furtherhydroprocessing or other processing in another reactor in a refinery(such as by using deasphalted oil product 255 as a heavy vacuum gas oilfeed), or the deasphalted oil product 255 can be used as a fuel oil.

FIG. 2 also shows an optional recycle 232 of a portion of the distillateproduct for combination with the other portions used as feed to thehydroprocessing reaction 110. The optional distillate recycle component232 can provide further solvent for use improving hydroprocessingreaction 110. Optionally, distillate recycle component 232 cancorrespond to a recycle of a portion of the distillate product, such asa recycle of a kerosene fraction of the distillate product.

FIG. 3 shows another process embodiment of the invention thatincorporates a solvent deasphalting unit. In the configuration shown inFIG. 3, a vacuum distillation tower is not used. Instead, the bottomsfraction 133 from atmospheric distillation unit 130 is passed into asolvent deasphalting unit 350. This results in a deasphalted atmosphericbottoms product 355 and an asphalt product 353. The configuration shownin FIG. 3 can be beneficial for reducing energy consumption, as vacuumdistillation is one of the more energy intensive processes in arefinery.

Additionally, the configuration shown in either FIG. 2 or FIG. 3 can beuseful for allowing segregation of low hydrogen to carbon ratiomolecules into a residual product (such as the asphalt product) whileusing milder reaction conditions that convert about 50 wt % to about 70wt % of the 1050° F.+ (566° C.+) portion of the feedstock. To achieve acomparable amount of segregation of low hydrogen to carbon ratiomolecules using hydroprocessing, conversion levels of at least 80 wt %or more of the 1050° F.+ (566° C.+) portion of the feedstock may beneeded.

FIG. 4 shows yet another process embodiment of the invention thatincorporates a solvent deasphalting unit. The type of configurationshown in FIG. 4 is useful for reducing the amount of fuel oil and otherhigher boiling products in favor of generation of more fuels and otherdistillate products. In FIG. 4, the bottoms fraction 443 from vacuumdistillation 140 is recycled and combined with a portion of the inputfeedstock 405. The combined vacuum bottoms and a first portion offeedstock 405 are passed into a solvent deasphalting unit 450. Thisresults in an asphalt product 453 and a deasphalted feed 415. Thedeasphalted feed 415 is then combined with a second portion 465 of thefeedstock. A portion of the liquid effluent from hydroprocessing 122 isalso added to this combination of feedstock materials. The combinationof feedstock materials is then hydroprocessed 110 according to any ofthe various conditions described herein.

PROCESS EXAMPLES Example 1

A fixed bed reactor was constructed from ¼ inch stainless steel tubing.The reactor included two 50 cm brass half cylinders that were boltedonto a ¼ inch stainless steel tube. The volume of the hot zone insidethe brass cylinder was 6.0 cc's. A fixed bed reactor was loaded with ahomogeneous blended mixture of 5.6 cc of 15-40 mesh sand and 1.4 cc of asupported NiMo hydroprocessing catalyst sized to 20-40 mesh. The blendedmixture was centered on the hot zone. The rest of the reactor tube (thecold zones at the top and bottom of the reactor tube) was filled with15-40 mesh sand. The supported NiMo catalyst was typical of those usedcommercially for removing metals from heavy oil feedstocks and had amedian pore size of greater than 150 Å. The reactor was mounted into afixed bed, upflow pilot unit. The fresh feedstock was 95 wt % Athabascabitumen/5 wt % of partially hydrogenated 1-methylnaphthalene (0.95 g/ccat 60° F. or 16° C.). The 5 wt % of 1-methylnaphthalene was added tofacilitate the start of the process run until recycled liquid productwas available for use as a solvent. 16 wt % of the fresh feedstock wasblended with 84 wt % of the C₆+ liquid produced by the process (thetotal liquid product or TLP). The bitumen feedstock contained 40 vol %of 1050° F.+ (566° C.+) resid. The sulfur, nitrogen, and oxygen contentswere 4.75 wt %, 0.5 wt %, and 0.2 wt % respectively. The API gravity was10 (1.0 g/cc). The feedstock contained 40 wppm nickel, 100 wppmvanadium, 8 wppm iron, and 5 wppm of other ash-forming elements. Processconditions were a hydrogen treat gas flow rate of 670 SCF/B (about 110Nm³/m³) of hydrogen, a temperature of 430° C., a total liquid feedstockflow rate of 21 cc/hr (corresponds to 2.5 hr⁻¹ LHSV based on volume offresh bitumen per volume of NiMo hydroprocessing catalyst per hour), anda total pressure of 800 psig (5.5 MPag).

The product from the unit was run through a hot separator held at 50° C.followed by a cold knock-out pot held at 5° C. The total liquid productrecovered had a mass between 93 and 95% of the mass of the liquid feed.The volume and composition of the unit offgas were measured. Bothhydrogen consumption and the extent of sulfur removal were alsomeasured. The unit ran smoothly for 25 days (1500 volumes of freshbitumen per volume of NiMo hydroprocessing catalyst) and then pluggeddue to deposition of coke and metals on the catalyst bed.

The API gravity of the bitumen feed was 13. The API gravity of the C₆+total liquid product was 18.

Example 2(Comparative)

A fixed bed reactor was constructed from ¼ inch stainless steel tubing.The reactor included two 50 cm brass half cylinders that were boltedonto a ¼ inch stainless steel tube. The volume of the hot zone insidethe brass cylinder was 6.0 cc's. A fixed bed reactor was loaded with ahomogeneous blended mixture of 4.2 cc of 15-40 mesh sand and 2.8 cc of asupported NiMo hydroprocessing catalyst sized to 20-40 mesh. The blendedmixture was centered on the hot zone. The rest of the reactor tube (thecold zones at the top and bottom of the reactor tube) was filled with15-40 mesh sand. The supported NiMo catalyst was typical of those usedcommercially for removing metals from heavy oil feedstocks and had amedian pore size of greater than 150 Å. The reactor was mounted into afixed bed, upflow pilot unit. The feedstock was 70 wt % Athabascabitumen/30 wt % of partially hydrogenated 1-methylnaphthatene (0.95 g/ccat 60° F.). The bitumen feedstock contained 40 vol % 1050+ resid. Thesulfur, nitrogen, and oxygen contents were 4.75 wt %, 0.5 wt %, and 0.2wt % respectively. The API gravity was 10 (1.0 g/cc). The feedstockcontained 40 wppm nickel, 100 wppm vanadium, 8 wppm iron, and 5 wppmother ash-forming elements. Process conditions were a hydrogen treat gasflow rate of 670 SCF/B (about 110 Nm³/m³) of hydrogen, a temperature of430° C., a total liquid feedstock flow rate of 21 cc/hr (corresponds to2.0 hr LHSV based on volume of fresh bitumen per volume of NiMohydroprocessing catalyst per hour), and a total pressure of 800 psig(5.5 MPag).

The product from the unit was run through a hot separator held at 50° C.followed by a cold knock-out pot held at 5° C. The total liquid productrecovered had a mass between 93 and 95% of the mass of the liquid feed.The volume and composition of the unit offgas was measured. Bothhydrogen consumption and the extent of sulfur removal were measured. Theunit ran smoothly for 18 days (900 volumes of fresh bitumen per volumeof NiMo hydroprocessing catalyst) and then plugged due to deposition ofcoke and metals on the catalyst bed.

The API gravity of the bitumen feed was 13. The API gravity of the C₄+total liquid product was 18.

Based on a comparison of examples 1 and 2, using a recycled portion ofthe total liquid product provided a superior performance vs.once-through operation with a solvent. The cycle length was extendedfrom 900 volumes of fresh bitumen per volume of hydroprocessing catalystto 1500 volumes of fresh bitumen per volume of catalyst. Thus, eventhough the ratio of recycle solvent to feedstock was greater than theratio of added solvent (1-methylnaphthalene) to feedstock, the amount offresh bitumen processed using the recycle solvent was still greater.

Example 3

A fixed bed, upflow reactor was constructed from ⅜^(th) inch stainlesssteel tubing. Two 50 cm brass half cylinders were bolted onto the ⅜^(th)inch tube. The volume of the hot zone inside the brass cylinder was 16.0cc's. The reactor was loaded with 3 g (4.9 cc) of a supported NiMohydroprocessing catalyst on top of 9 g (8.1 cc) of a commerciallyavailable bulk NiMoW hydroprocessing catalyst. The supported. NiMocatalyst was used primarily for removing metals from heavy oilfeedstocks and had a median pore size of greater than 150 Å. The medianpore diameter of the bulk NiMoW catalyst was 94 Å, as shown in Table 1below. The catalyst system was sulfided using a feedstock comprised of80 wt % 130-neutral lube oil/20 wt % ethyl-disulfide.

The feedstock for sulfiding the catalyst system was processed at 3000SCF/B (standard cubic feet of hydrogen per barrel of feed, about 500Nm³/m³), at 340° C. (644° F.), 0.17 LHSV (liquid hourly space velocity),and 1000 psig (6895 kPa) for 48 hours. The feedstock was then switchedto 60 wt % Athabasca bitumen/40 wt % trimethylbenzene (TMB). Reactionconditions were changed to 800 psig (5516 kPa-g), cc/hr liquid feed(corresponding to an LHSV of 0.39 volumes of fresh bitumen per volume ofbulk NiMoW hydroprocessing catalyst per hour), and 1100 SCF/B hydrogen(197 S m³/m³). The reactor temperature was varied between 689° F. (365°C.) and 780° F. (416° C.).

The Athabasca bitumen had the following properties: 4.8 wt % S, 5000wppm N, 55% wt % of the feed having a boiling point between 450° F. to1050° F. (232° C. to 566° C.), 45 wt % of the feed corresponding to a1050° F.+ (566° C.+) fraction, 0.9950 specific gravity at 60° F. (15.6°C.), 67 wppm Ni, 166 wppm V, and 13 wppm Fe.

During the run, the hydrodesulfurization and hydrodemetallization levelswere typically held between 60 and 70% through temperature adjustment.The deposition of metals in the reactor was tracked with time. Forexample, at the time that the catalyst had accumulated 5 wt % metals,the conditions were 800 psig (5516 kPa-g) and 725° F. (385° C.). Lessthan 1 wt % of the TMB was hydrogenated and/or hydrocracked.

The catalyst was run for 150 days, resulting in processing of 2368volumes of bitumen per volume of NiMoW hydroprocessing catalyst. The HDSactivity of the catalyst dropped by less than 1% over a 3 week period ata temperature as high as 780° F. (416° C.). The run was voluntarilyterminated to enable examination of the metals distribution on thecatalyst before metal loading filled any more of the catalyst voidvolume.

Upon ending the run, the catalysts were analyzed for vanadium profile inthe extrudates. The vanadium deposit across whole extrudates was foundto be evenly deposited throughout the extrudate on both catalysts, whichwas indicative of an insignificant presence of pore mouth plugging.Analysis of the spent catalysts showed that the metals uptake of bothcatalysts were similar, at about 0.14 g metal/cc of catalyst.

This example demonstrates that upgrading of Athabasca bitumen in thepresence of TMB as a solvent, a single-ring aromatic compound, at amoderate pressure of 800 psig (5516 kPa-g) can be achieved for anextended period of time without reactor plugging problems. Moreover,there is little metal buildup inside catalyst pores.

Example 4(Comparative)

A fixed bed reactor similar to the reactor described in Example 3 wasused. The reactor included two 50 cm brass half cylinders that werebolted onto a ⅜^(th) inch stainless steel tube. The volume of the hotzone inside the brass cylinder was identical to example 3. The volume ofthe hot zone inside the brass cylinder was 16.0 cc's. The reactor wasloaded with 3 g (4.9 cc) of a supported NiMo hydroprocessing catalystwith a median pore diameter of greater than 150 Å on top of 9 g (7.6 cc)of a commercially available bulk NiMoW hydroprocessing catalyst with amedian pore diameter of 94 Å. The supported NiMo catalyst was usedprimarily for removing metals from heavy oil feedstocks. The catalystsystem was sulfided using a feedstock comprised of 80 wt % 130-neutrallube oil/20 wt % ethyl-disulfide.

The feedstock for sulfiding the catalyst system was processed at 3000SCF/B (standard cubic feet of hydrogen per barrel of feed), at 340° C.(644° F.), 0.12 LHSV (liquid hourly space velocity), and 1000 psig (6895kPa) for 48 hours. The feedstock was then switched to 95 wt % Athabascabitumen and 5 wt % toluene. Reaction conditions were changed to 800 psig(5516 kPa-g), 5 cc/hr liquid feed (corresponding to an LHSV of 0.62volumes of bitumen per volume of NiMoW catalyst per hour), and 1100SCF/13 hydrogen (197 S m³/m³). The reactor temperature was kept at 725°F. (385° C.).

The Athabasca bitumen had the following properties: 4.8 wt % S, 5000wppm N, 55% wt % of the feed having a boiling point between 450° F. to1050° F. (232° C. to 566° C.), 45 wt % of the feed corresponding to a1050° F.+ (566° C.+) fraction, 0.9950 specific gravity at 60° F. (15.6°C.), 67 wppm. Ni, 166 wppm V, and 13 wppm Fe. The reactor failed onpressure drop after 11.3 days of operation, which corresponds toprocessing of 57 volumes of bitumen per volume of NiMoW hydroprocessingcatalyst before failure.

Table 1 provides a summary of these lifetime characterization runs inexample 3 and 4.

TABLE 1 Catalyst Lifetime Dependence on Solvent Vol Resid/Vol AVG poresize Catalyst Feed Catalyst (Angstroms) Dual catalyst - 60% Athabasca2368 (150 days at 94 (small pore) Example 3 bitumen/40% TMB 0.39 LHSV)Dual catalyst - 95% Athabasca 57 (11.3 days at 94 (small pore) Example 4bitumen/5% toluene 0.62 LHSV)

Example 5

A fixed bed reactor similar to the reactor described in Example 3 wasused. The reactor included two 50 cm brass half cylinders that werebolted onto a ⅜″ inch stainless steel tube. The volume of the hot zoneinside the brass cylinder was 16.0 cc's. The center of the 16 cc hotzone was loaded with 5 cc's of a commercially available large poreNiMo/Al₂O₃ demetallation catalyst with a median pore diameter of greaterthan 150 Å followed by 7.6 cc's (9 g) of a commercially available bulkNiMoW catalyst (similar to the catalyst from Example 2) with a medianpore diameter of about 94 Å. The catalyst was mounted into a standarddown-flow pilot unit, and sulfided using standard procedures.

Athabasca bitumen was hydrotreated. The Athabasca bitumen had thefollowing properties: 4.8 wt % S, 5000 wppm N, 55% wt % of the feedhaving a boiling point between 450° F. to 1050° F. (232° C. to 566° C.),45 wt % of the feed corresponding to a 1050° F.+ (566° C.+) fraction,0.9950 specific gravity at 60° F. (15.6° C.), 67 wppm. Ni, 166 wppm V,and 13 wppm Fe. A feedstock was blended from 60 wt % Athabasca bitumenand 40 wt % 1,2,4-trimethylbenzene. A process variable study wasconducted within the following condition window: 2-10 cc/hr liquid feed,6-30 sccm hydrogen, 365-395° C. Pressure was constant at 800 psig (5.5MPag). The deposition of metals in the reactor was tracked with time. Atthe time that the catalyst had accumulated 5 wt % metals, the producteffluent at these conditions was analyzed using standard testingmethods, 1050° F.+ (566° C.+) conversion was 23%, the amount of sulfurremoval was 62%, and the amount of metals removal was 66%.

Example 6(Comparative)

A fixed bed reactor similar to the reactor described in Example 3 wasused. The reactor included two 50 cm brass half cylinders that werebolted onto a ⅜^(th) inch stainless steel tube. The volume of the hotzone inside the brass cylinder was 21.0 cc's. The center of the 21 cchot zone was loaded with 7 cc's (4.2 g) of a commercially availablelarge pore NiMo/Al₂O₃ demetallation catalyst having a median pore sizegreater than 150 Å followed by 14 cc's (10.9 g) of a commerciallyavailable CoMo/Al₂O₃ hydroprocessing catalyst with a median pore size ofat least about 150 Å. The catalyst was mounted into a standard down-flowpilot unit, and sulfided using standard procedures.

Athabasca bitumen was hydrotreated. The Athabasca bitumen had thefollowing properties: 4.8 wt % S, 5000 wppm N, 55% wt % of the feedhaving a boiling point between 450° F. to 1050° F. (232° C. to 566° C.),45 wt % of the feed corresponding to a 1050° F.+ (566° C.+) fraction,0.9950 specific gravity at 60° F. (15.6° C.), 67 wppm. Ni, 166 wppm V,and 13 wppm Fe. A feedstock was blended from 60 wt % Athabasca bitumenand 40 wt % 1,2,4-trimethylbenzene. A process variable study wasconducted within the following condition window: 2-10 cc/hr liquid feed,6-30 sccm hydrogen, 365-395° C. Pressure was constant at 800 psig (5.5MPag). The deposition of metals in the reactor was tracked with time. Atthe time that the catalyst was estimated to have accumulated 5 wt %metals, the product effluent at these conditions was analyzed usingstandard testing methods. 1050° F.+ (566° C.+) conversion was 15%, theamount of sulfur removal was 71%, and the amount of metals removal was74%.

Table 2 shows a comparison of the catalyst activities for the catalystsystem including a small pore catalyst in Example 5 and a catalystsystem using a large pore catalyst in Example 6. Comparison of Examples5 and 6 demonstrate that the small pore (85 Å to 120 Å) hydroprocessingcatalyst was roughly 50% more active for conversion of the 1050° F.+(566° C.+) portion of the feed as the conventional larger pore (>150 Åmedian pore size) resid hydroprocessing catalyst. On a volume basis, thesmall pore catalyst was also about twice as active as the large porecatalyst for desulfurization and demetallation, while on a volume basisthe activities of the small pore catalyst and large pore catalyst werecomparable. It is unexpected that a large pore catalyst designed toprocess resid would be less active than a small pore catalyst. It isalso unexpected that vanadium is evenly distributed across the extrudateof a high activity, small pore hydrodesulfurization catalyst.

TABLE 2 Comparison of Small Pore and Large Pore Activities 1050° F.+Catalyst Catalyst (566° C.+) Catalyst Weight Volume Conversion ExampleConfiguration (2^(nd) catalyst) (2^(nd) Catalyst) (wt %) 5 Large pore/  9 g 7.6 cc 23 Small pore 6 Large pore/ 10.9 g  14 cc 15 Large pore

As shown in Table 1, use of a diluent provides about a factor of 40improvement in catalyst lifetime. Conventionally, large porehydroprocessing catalysts are believed to be superior tierhydroprocessing of heavy oil feeds. However, as shown in Table 2 basedon Examples 5 and 6, with an appropriate solvent, the catalyst systemincluding the small pore hydroprocessing catalyst exhibited either acomparable or superior activity over the large pore hydroprocessingcatalyst depending on the desired type of activity. This allows for useof a lesser amount of small pore catalyst while still achieving similarprocessing results.

Example 7

A fixed bed reactor was constructed from ⅜^(th) inch stainless steeltubing. The reactor included two 50 cm brass half cylinders that werebolted onto a ⅜^(th) inch stainless steel tube. The volume of the hotzone inside the brass cylinder was 12.0 cc's. 23 cc's (27 g) of acommercially available bulk NiMoW catalyst similar to the catalyst fromExample 3) with a median pore size of about 94 Å was loaded tocompletely fill the hot zone inside the brass cylinder and the entirerest of reactor volume in front of and in back of the hot zone. Thecatalyst was mounted into a standard down-flow pilot unit, and sulfidedusing standard procedures.

A feedstock was blended from 60 wt % of a demetallized 950° F.+ (510°C.+) vacuum resid and 40 wt % of recycled 300-600° F. (149-316° C.)distillate product (0.955 g/cc at 60° F.). The demetallized 950° F.+(510° C.+) vacuum resid (no solvent) contained 20 wppm metals, 0.6 wt %sulfur, and 13 wt % hydrogen. 84% of the demetallized resid correspondedto material with a boiling point of 1050° F.+ (566° C.+). Thedemetallized vacuum resid was formed from distillation of a whole crudeoil that was 18 wt % wax as measured by differential scanningcalorimetry. The demetallized vacuum resid feedstock was pumped into thereactor at 3.0 cc/hr along with 10 seem of hydrogen (1150 SCF/B of feed,about 195 Nm³/m³). The reactor was held at 445° C. The product effluentwas analyzed using standard testing methods. The reactor consumed 360SCF/B (about 60 Nm³/m³) of hydrogen, which corresponds to 600 SCF/B(about 100 Nm³/m³) relative to the demetallized 950° F.+ (510° C.+)vacuum resid, and corresponds to one third of the 1150 SCF/B (about 195Nm³/m³) of hydrogen fed to the reactor. Less than 5 wt % of the recycleddistillate was converted to products outside the distillate boilingrange, making the yield of recycled distillate feed in the productbetween 38 and 40 wt %.

After removing and/or accounting for the recycled distillate cofeed,product yields from conversion of the demetallized 950° F.+ (510° C.+)vacuum resid were: 0.7 wt % H₂S; 5 wt % methane plus ethane; 5 wt %propane plus butanes; 20 wt % naphtha (C₅-400° F.); 37 wt % distillate(400° F.-650° F.); 24 wt % vacuum gas oil (650° F.-1050° F.; 343°C.-566° C.) and 8 wt % 1050° F.+ (566° C.+) material. The 1050° F. (566°C.) conversion of the demetallized feed was 90%, the amount of sulfurremoval was 99%, and the amount of metals removal was >99%. In preferredembodiments of the invention, the 1050° F.+ (566° C.+) conversion of thefeed in the final liquid products from the primary reaction (i.e.,“liquid effluent”) is at least 80 wt %, more preferably at least 90 wt %or at least 95 wt %. In preferred embodiments of the invention, theamount of sulfur in the final liquid products (i.e., “liquid effluent”)is less than 20 wt %, more preferably less than 10 wt %, less than 5 wt%, or most preferably, less than 1 wt % of the sulfur in the heavy oilfeed. In preferred embodiments of the invention, the amount of metals inthe final liquid products (i.e., “liquid effluent”) is less than 20 wt%, more preferably less than 10 wt %, less than 5 wt %, or mostpreferably, less than 1 wt % of the metals in the heavy oil feed. A verylow sulfur Bunker C Fuel Oil as described prior, can be made as aproduct from the vacuum gas oil and/or vacuum bottoms (1050° F.+)streams in this process.

Returning to the example, the total liquid product was subjected tovacuum distillation. A 20% yield of 800+° F. (427° C.+) product wasisolated by vacuum distillation. Surprisingly, the recovered 800+° F.(427° C.+) product was highly enriched in wax and polynuclear aromaticcores. Detailed analysis of the sample found that two thirds of themolecules were highly enriched in wax and one-third of the moleculeswere dealkylated polynuclear aromatics. NMR analysis found that 67% ofthe carbons in the dealkylated polynuclear aromatic molecules werearomatic, and less than 5 wt % of the carbons in the polynucleararomatics were in sidechains with >8 carbons. Two thirds of thealiphatic protons in the polynuclear aromatics were either methyl groupsor in CH and CH₂ groups attached to an aromatic ring. The fractionhighly enriched in wax was found to contain 20 wt % n-paraffin(unbranched) wax and 10 wt % mono-methyl paraffin wax. The n-paraffinwax+monomethyl paraffin wax was concentrated in the 800° F.-1000° F.(427° C.-538° C.) boiling range (C₃₀ to C₄₀). Surprisingly, the fractionenriched in wax also contained a lot of aromatic molecules. NMR analysisof the fraction found that 25% of the carbons were aromatic and 22% ofthe carbons were epsilon carbons. The C₄₀+ molecules boiling above 1000°F. (538° C.) were enriched in aromatic molecules. The availableanalytical data indicates that more than half of the 1000° F.+ (538°C.+) molecules are benzene, naphthalene, and three-fused ring aromaticswith long side chains (aromatic waxes).

It is surprising that a relatively simple, easily separated mixture ofmolecules was formed from hydroprocessing of crude oil vacuum resid. Theexample provides a method for producing conventional paraffin wax and anunusual 1000° F.+ (538° C.+) aromatic wax from resid.

The wax in the 800° F.+ (427° C.+) fraction can be separated out by anyconvenient method. After separation of the wax, the remaining portion ofthe 800° F.+ (427° C.+) fraction can be used as a low sulfur fuel oil.Based on the 99% sulfur removal, the amount of sulfur remaining in theproduct is about 0.03 wt % or less, which is below the desired target ofless than 1 wt % sulfur for a low sulfur fuel oil. In an alternativeembodiment, the 800° F.+ fraction can be used as a low sulfur fuel oilwithout performing a prior wax separation.

In this example, a distillate product with a boiling range of 300° F.(149° C.) to 600° F. (316° C.) was recycled for use as a solvent. Inother embodiments, other distillate products suitable for use as asolvent include a distillate product where 90 wt % of the distillateproduct boils in a boiling range of 300° F. (149° C.) to 550° F. (288°C.); or 300° F. (149° C.) to 600° F. (316° C.); or 300° F. (149° C.) to750° F. (399° C.); or 400° F. (204° C.) to 750° F. (399° C.).

Example 8

In this example, processes involving conversion of a lower percentage offeed followed by solvent deasphalting were compared with processesinvolving conversion of a higher percentage of a feed. In this example,processes involving deasphalting were performed using a configurationsimilar to FIG. 2 (atmospheric and vacuum distillation of hydroprocessedeffluent follow by deasphalting of bottoms), while a comparative set ofprocesses were performed using a configuration similar to FIG. 1.

In this example, a resid feedstock was processed under several types ofconditions. The resid feedstock was a 650° F.+ (343° C.+) resid thatcontained 110 ppm of metals, 4.6 wt % sulfur, and 9.75 wt % hydrogen.The 1050° F.+ (566° C.+) portion of the resid feedstock corresponded to42 wt % of the feed. The resid feedstock was used to form a combinedfeedstock containing 60 wt % of the resid feed and 40 wt % oftrimethylbenzene as a solvent. The combined feedstock was processedunder two types of hydroprocessing conditions. In a first set of processconditions, the resid feedstock was hydroprocessed to achieve about 66%conversion of the 1050° F.+ (566° C.+) portion of the feed with TMBsolvent that operated for over 100 days at >60% conversion. In a secondset of process conditions, the resid feedstock was processed to achieveabout 88% conversion of the 1050° F.+ (566° C.+) portion of the feed. Itis noted that under the second process conditions, the catalystdeactivated rapidly over 14 days of operation, indicating that thesystem was unstable under the higher severity process conditions evenwith the aid of the trimethylbenzene solvent.

Table 3 shows the product comparison from various ways of fractionatingproducts from the two types of processes. In Table 3, the first row isshowing the hydrogen content of the 1050° F.+ (566° C.+) portion of thefeed, so the weight percentage of 1050° F.+ (566° C.+) is 100%. As shownin Table 3, a substantial amount of molecules with relatively largehydrogen to carbon ratios are present in the feed, based on the hydrogento carbon ratio in the 1050° F.+ (566° C.+) portion of the feed of 1.43.

In order to separate the more valuable (i.e., higher hydrogen content)molecules in the 1050° F.+ (566° C.+) portion of the feed from moleculeswith lower hydrogen to carbon ratios, one option is to select severehydroprocessing conditions for processing of the feed, such asconditions sufficient to convert 88% of the 1050° F.+ (566° C.+) portionof the feedstock. As shown in the final row of Table 3, at 88%conversion (which leaves behind only 12 wt % of 1050° F.+ or 566° C.+unconverted feed), some molecules with higher hydrogen to carbon ratiosare still present, but overall the hydroprocessing is fairly effectiveat creating an atmospheric resid that contains only lower valuemolecules with low hydrogen content, as indicated by the hydrogen tocarbon ratio of 0.80.

The results from hydroprocessing to achieve 66% conversion of the teedindicates that the remaining 34% of 1050° F.+ (566° C.+) materialcontains some good quality molecules, as the hydrogen to carbon ratio of1.37 is not that different from the 1.43 hydrogen to carbon ratio of the1050° F.+ (566° C.+) portion of the feed. However, the 1050° F.+ (566°C.+) portion (possibly formed as bottoms from a vacuum distillation) canthen be exposed to pentane deasphalting in order to form a deasphaltedoil and a C₅ deasphalting residue. After deasphalting, the deasphaltedoil fraction (28% of the original 1050° F.+ or 566° C.+ material in thefeed) has a hydrogen to carbon ratio of 1.48. By contrast, the C₅deasphalting residue (6% of the original 1050° F.+ or 566° C.+ material)has a hydrogen to carbon ratio of 0.89, which is similar to the hydrogento carbon ratio of 0.8 achieved under the processing conditions suitablefor 88% conversion of the feedstock.

TABLE 3 Hydrogen to Carbon Ratio of Processed Resid Fractions Wt YieldH/C (1050° F.+/566° C.+) Resid feed 1050° F.+ portion 1.43 100 66% 1050+conv 1.37 34 a) 66% 1050+ conv deasphalted oil 1.48 28.0 b) 66%1050+conv C₅ deasphalting 0.89 6.0 residue 88% 1050+ conversion 0.80 12

Based on these results, hydroprocessing under lower severity conditionsfollowed by deasphalting was able to perform a comparable segregation oflow hydrogen-to-carbon ratio molecules as performing hydroprocessing atmuch higher severity. In addition to reducing the hydrogen consumptionrequired for conversion of the feed, the lower severity hydroprocessingconditions also allow for greater run lengths.

Additional Embodiments

Embodiment 1. A process for producing a hydroprocessed product,comprising: exposing a combined feedstock comprising a heavy oil feedcomponent and a solvent component to a hydroprocessing catalystcomprising a Group VIII non-noble metal and a Group VI metal and havinga median pore size of about 85 Å to about 120 Å, under effectivehydroprocessing conditions to form a hydroprocessed effluent, theeffective hydroprocessing conditions including a total pressure of about1500 psig (10.3 MPag) or less, a temperature of at least about 360° C.,and a liquid hourly space velocity of the fraction of the combinedfeedstock boiling above 1050° F. (566° C.) of at least about 0.10 hr⁻¹;separating the hydroprocessing effluent to form at least a liquideffluent; and fractionating a first portion of the liquid effluent toform at least a distillate product and a bottoms product, the bottomsproduct having the bottoms product having an ASTM D6352 10% distillationpoint of at least about 600° F. (316° C.).

Embodiment 2. The process of Embodiment 1, wherein the solvent componentcomprises a recycle component, the process further comprising recyclinga second portion of the liquid effluent to form the recycle component.

Embodiment 3. The process of Embodiment 2, wherein the ratio of therecycle component or solvent component to the heavy oil feed componenton a weight basis is from about 0.3 to about 6.0, such as from about 0.5to about 5.0.

Embodiment 4. The process of any of the above embodiments, wherein theeffective hydroprocessing conditions comprise a partial pressure ofhydrogen of about 800 psia (5.5 MPa) or less and/or a partial pressureof hydrogen of at least about 400 psia (2.8 MPa) and/or a partialpressure of hydrogen of at least about 650 psia (4.5 MPa) and/or a totalpressure of about 1200 psig (8.3 Mpag) or less, or a total pressure ofabout 1000 psig (6.9 MPag) or less, or a total pressure of about 800psig (5.5 MPag) or less.

Embodiment 5. The process of any of the above embodiments, wherein theheavy oil feed component has an ASTM D6352 10% distillation point of atleast 650° F. (343° C.), such as at least 750° F. (399° C.), or at least900° F. (482° C.), or at least 950° F. (510° C.).

Embodiment 6. The process of any of the above embodiments, wherein theliquid hourly space velocity of the fraction of the combined feedstockboiling above 1050° F. (566° C.) is at least about 0.12 hr⁻¹, such as atleast about 0.18 hr⁻¹.

Embodiment 7. The process of any of the above embodiments, furthercomprising performing solvent deasphalting on at least a portion of thebottoms product to form a deasphalted bottoms product and an asphaltproduct.

Embodiment 8. The process of Embodiment 7, wherein the effectivehydroprocessing conditions are effective for conversion of from about 50to about 70% of the 1050° F. (566° C.+) portion of the heavy oil feedcomponent.

Embodiment 9. The process of Embodiment 8, further comprising performinga vacuum fractionation on at least a portion of the bottoms product toform at least a vacuum gas oil product and a vacuum bottoms product,wherein solvent deasphalting is performed on at least a portion of thevacuum bottoms product.

Embodiment 10. The process of Embodiment 9, wherein the heavy oil feedcomponent comprises a first heavy oil feed portion and a second heavyoil feed portion, the method further comprising combining the vacuumbottoms product with the first heavy oil feed portion prior to solventdeasphalting, wherein the combined feedstock comprises the deasphaltedbottoms product, the second heavy oil feed portion, and the solventcomponent.

Embodiment 11. The process of any of the above embodiments, wherein thesolvent comprises at least a portion of the distillate product, at least90 wt % of the at least a portion of the distillate product having aboiling point in a boiling range of 300° F. (149° C.) to 750° F. (399°C.), or in a boiling range of 300° F. (149° C.) to 600° F. (316° C.), orin a boiling range of 400° F. (204° C.) to 750° F. (399° C.).

Embodiment 12. The process of Embodiment 11, wherein 10 wt % or less,and preferably 5 wt % or less, of the at least a portion of thedistillate product in the combined feedstock is converted to componentshaving a boiling point of less than 300° F. during exposure of thecombined feedstock to the effective hydroprocessing conditions.

Embodiment 13. The process of any of the above embodiments, wherein thesolvent component comprises at least one single ring aromatic compoundin which the solvent has an ASTM D86 10% distillation point of at least120° C. (248° F.) and a 90% distillation point of not greater than 300°C. (572° F.).

Embodiment 14. The process of Embodiment 13, wherein the solventcomponent comprises more than one single-ring aromatic compound and noneof the single-ring aromatic compounds has a boiling point of greaterthan 550° F. (288° C.).

Embodiment 15. The process of Embodiment 13 or 14, wherein the solventcomponent is comprised of at least 50 wt % of one or more single ringaromatic compounds.

Embodiment 16. The process of any of Embodiments 13-15, wherein at leastone single-ring aromatic compound is trimethylbenzene.

Embodiment 17. The process of any of the above embodiments, wherein theheavy oil feed component has ASTM D6352 10% distillation point of atleast 900° F. (482° C.), such as at least 950° F. (510° C.), theeffective hydroprocessing conditions further comprising a temperature ofat least about 420° C., such as at least 440° C., and a hydrogen partialpressure of about 1000 psia (6.9 MPa) or less, the effectivehydroprocessing conditions being effective for at least about 90%conversion of the 1050° F.+ (566° C.+) portion of the combinedfeedstock, and wherein the bottoms product has a T5 boiling point of atleast about 650° F. (343° C.), such as at least about 750° F. (399° C.)or 800° F. (427° C.), a concentration of wax in the bottoms productbeing greater than a concentration of wax in the heavy oil feedcomponent of the combined feedstock.

Embodiment 18. The process of any of the above embodiments, wherein theeffective hydroprocessing conditions further comprising a temperature ofat least about 420° C. such as about 440° C., the effectivehydroprocessing conditions being effective for at least about 80%conversion of the 1050° F.+ (566° C.+) portion of the combinedfeedstock, such as at least about 90% conversion, and at least about 75%desulfurization of the combined feedstock, such as at least about 80%desulfurization, and wherein the bottoms product has an ASTM D6352 10%distillation point of at least about 800° F. (427° C.) and a sulfurcontent of about 1.0 wt % or less.

Embodiment 19. The process of Embodiment 18, wherein the heavy oil feedcomponent has an ASTM D6352 10% distillation point of at least 900° F.(482° C.), such as at least 950° F.

Embodiment 20. The process of any of the above embodiments, wherein thehydroprocessing catalyst is a bulk catalyst.

Embodiment 21. The process of any of the above embodiments, wherein thehydroprocessing catalyst has a median pore size of about 85 Å to about100 Å.

The principles and modes of operation of this invention have beendescribed above with reference to various exemplary and preferredembodiments. As understood by those of skill in the art, the overallinvention, as defined by the claims, encompasses other preferredembodiments not specifically enumerated herein.

The invention claimed is:
 1. A process for producing a hydroprocessedproduct, comprising: exposing a combined feedstock comprising a heavyoil feed component and a solvent component to a bulk metalhydroprocessing catalyst comprising a Group VIII non-noble metal and aGroup VI metal and having a median pore size of about 85 Å to about 120Å, under effective fixed bed hydroprocessing conditions to form ahydroprocessed effluent, the effective hydroprocessing conditionsincluding a total pressure of about 1500 psig (10.3 MPag) or less, atemperature of at least about 360° C., and a liquid hourly spacevelocity of the fraction of the combined feedstock boiling above 1050°F. (566° C.) of at least about 0.10 hr⁻¹, the heavy oil feed componenthaving an n-pentane asphaltene content of at least about 5 wt %;separating the hydroprocessing effluent to form at least a liquideffluent; and fractionating a first portion of the liquid effluent toform at least a distillate product and a bottoms product, the bottomsproduct having an ASTM D6352 distillation point of at least about 600°F. (316° C.).
 2. The process of claim 1, the hydroprocessing catalysthaving a median pore size of about 85 Å to about 100 Å.
 3. The processof claim 1, wherein the solvent component comprises a recycle component,the process further comprising recycling a second portion of the liquideffluent to form the recycle component.
 4. The process of claim 3,wherein the ratio of the recycle component to the heavy oil feedcomponent on a weight basis is from about 0.3 to about 6.0.
 5. Theprocess of claim 1, wherein the effective hydroprocessing conditionscomprise a partial pressure of hydrogen of about 800 psia (5.5 MPa) orless, a total pressure of about 1000 psig (6.9 MPag) or less, or acombination thereof.
 6. The process of claim 1, wherein the liquidhourly space velocity of the fraction of the combined feedstock boilingabove 1050° F. (566° C.) is at least about 0.12 hr⁻¹.
 7. The process ofclaim 1, further comprising performing solvent deasphalting on at leasta portion of the bottoms product to form a deasphalted bottoms productand an asphalt product, wherein the effective hydroprocessing conditionscomprise a pressure of about 1000 psig (6.9 MPag) or less.
 8. Theprocess of claim 7, wherein the effective hydroprocessing conditions areeffective for conversion of about 50 wt % to about 70 wt % of the 1050°F.+ (566° C.+) portion of the heavy oil feed component.
 9. The processof claim 8, further comprising performing a vacuum fractionation on atleast a portion of the bottoms product to form at least a vacuum gas oilproduct and a vacuum bottoms product, wherein solvent deasphalting isperformed on at least a portion of the vacuum bottoms product.
 10. Theprocess of claim 9, wherein the heavy oil feed component comprises afirst heavy oil feed portion and a second heavy oil feed portion, themethod further comprising combining the vacuum bottoms product with thefirst heavy oil feed portion prior to solvent deasphalting, wherein thecombined feedstock comprises the deasphalted bottoms product, the secondheavy oil feed portion, and the solvent component.
 11. The process ofclaim 1, wherein the solvent comprises at least a portion of thedistillate product, at least 90 wt % of the at least a portion of thedistillate product having a boiling point in a boiling range of 300° F.(149° C.) to 750° F. (399° C.).
 12. The process of claim 1, wherein thesolvent component comprises at least one single ring aromatic compoundin which the solvent has an ASTM D86 10% distillation point of at least120° C. (248° F.) and a 90% distillation point of not greater than 300°C. (572° F.).
 13. The process of claim 12, wherein the solvent componentcomprises more than one single-ring aromatic compound and none of thesingle-ring aromatic compounds has a boiling point of greater than 550°F. (288° C.), or wherein the solvent component is comprised of at least50 wt % of one or more single ring aromatic compounds, or a combinationthereof.
 14. The process of claim 12, wherein the at least onesingle-ring aromatic compound is trimethylbenzene.
 15. The process ofclaim 1, wherein the heavy oil feed component has ASTM D6352 10%distillation point of at least 900° F. (482° C.), the effectivehydroprocessing conditions comprising a temperature of at least about420° C. and a hydrogen partial pressure of about 1000 psia (6.9 MPa) orless, the effective hydroprocessing conditions being effective for atleast about 90% conversion of the 1050° F. + (566° C.+) portion of thecombined feedstock, and wherein the bottoms product has an ASTM D635210% distillation point of at least about 650° F. (343° C.), aconcentration of wax in the bottoms product being greater than aconcentration of wax in the heavy oil feed component of the combinedfeedstock.
 16. The process of claim 15, wherein the effectivehydroprocessing conditions comprise a temperature of at least about 440°C.
 17. The process of claim 1, wherein the effective hydroprocessingconditions further comprise a temperature of at least about 420° C., theeffective hydroprocessing conditions being effective for at least about80% conversion of the 1050° F.+ (566° C.+) portion of the combinedfeedstock and at least about 75% desulfurization of the combinedfeedstock, and wherein the bottoms product has an ASTM D6352 10%distillation point of at least about 800° F. (427° C.) and a sulfurcontent of about 1.0 wt % or less.
 18. The process of claim 17, whereinthe heavy oil feed component has an ASTM D6352 10% distillation point ofat least 900° F. (482° C.).
 19. The process of claim 18, wherein theheavy oil feed component has a sulfur content of at least 3 wt %. 20.The process of claim 19, wherein the liquid effluent has a sulfurcontent of less than 5 wt % of the heavy oil feed component and has ametals content of less than 5 wt % of the heavy oil feed component. 21.The process of claim 20, wherein the effective hydroprocessingconditions are effective for at least about 90% conversion of the 1050°F.+ (566° C.+) portion of the combined feedstock.
 22. The process ofclaim 1, further comprising performing a vacuum fractionation on atleast a portion of the bottoms product to form at least a vacuum gas oilproduct and a vacuum bottoms product, and producing a Bunker C Fuel Oilcontaining less than 1 wt % sulfur from at least a portion of the vacuumgas oil product.
 23. A process for producing a hydroprocessed product,comprising: exposing a combined feedstock comprising a heavy oil feedcomponent and a solvent component to a bulk metal hydroprocessingcatalyst comprising a Group VIII non-noble metal and a Group VI metaland having a median pore size of about 85 Å to about 120 Å, undereffective fixed bed hydroprocessing conditions to form a hydroprocessedeffluent, the effective hydroprocessing conditions including a totalpressure of about 1500 psig (10.3 MPag) or less, a temperature of atleast about 360° C., and a liquid hourly space velocity of the fractionof the combined feedstock boiling above 1050° F. (566° C.) of at leastabout 0.10 hr⁻¹, the heavy oil feed component having a content of atleast about 200 ppm per gram on a total elemental basis of nickel,vanadium and iron; separating the hydroprocessing effluent to form atleast a liquid effluent; and fractionating a first portion of the liquideffluent to form at least a distillate product and a bottoms product,the bottoms product having an ASTM D6352 distillation point of at leastabout 600° F. (316° C.).
 24. A process for producing a hydroprocessedproduct, comprising: exposing a combined feedstock comprising a heavyoil feed component and a solvent component to a bulk metalhydroprocessing catalyst comprising a Group VIII non-noble metal and aGroup VI metal and having a median pore size of about 85 Å to about 120Å, under effective fixed bed hydroprocessing conditions to form ahydroprocessed effluent, the effective hydroprocessing conditionsincluding a total pressure of about 1500 psig (10.3 MPag) or less, atemperature of at least about 360° C., and a liquid hourly spacevelocity of the fraction of the combined feedstock boiling above 1050°F. (566° C.) of at least about 0.10 hr⁻¹; separating the hydroprocessingeffluent to form at least a liquid effluent; and fractionating a firstportion of the liquid effluent to form at least a distillate product anda bottoms product, the bottoms product having an ASTM D6352 distillationpoint of at least about 600° F. (316° C.), wherein the heavy oil feedcomponent has ASTM D6352 10% distillation point of at least 900° F.(482° C.), the effective hydroprocessing conditions comprising atemperature of at least about 420° C. and a hydrogen partial pressure ofabout 1000 psia (6.9 MPa) or less, the effective hydroprocessingconditions being effective for at least about 90% conversion of the1050° F. + (566° C.+) portion of the combined feedstock, and wherein thebottoms product has an ASTM D6352 10% distillation point of at leastabout 650° F. (343° C.), a concentration of wax in the bottoms productbeing greater than a concentration of wax in the heavy oil feedcomponent of the combined feedstock.